Antifouling coating composition, antifouling film, composite film, and in-water structure

ABSTRACT

Provided are an antifouling coating composition that contains: a hydrolyzable resin having a specific silicon-containing group and a metal-atom-containing group containing a divalent metal atom M; and a thermoplastic resin and/or a plasticizer, wherein the total content of the thermoplastic resin and/or plasticizer per 100 parts by mass of the hydrolyzable resin is 3 to 100 parts by mass, an antifouling film, a composite film and an in-water structure such as a ship using the antifouling coating composition. The antifouling coating composition makes it possible to form a coating film that is excellent in crack resistance and exhibits a good antifouling property over a long period of time even when no antifouling agent is contained or the blending amount thereof is small.

TECHNICAL FIELD

The present invention relates to an antifouling coating composition, andmore specifically, to an antifouling coating composition containing ahydrolyzable resin that gradually dissolves in water by hydrolysis.Also, the present invention relates to an antifouling film formed fromthe antifouling coating composition and a composite film having theantifouling film, and an in-water structure such as a ship having theantifouling film or the composite film.

BACKGROUND ART

Organisms such as barnacles, mussels and algae are likely to adhere onships, fish nets, and other in-water structures. Such adhesion oforganisms will lead the problem of hindrance of efficient travel andwaste of the fuel in ships and the like. In fish nets and the like, theproblems of clogging and shortening of the service life arise.Conventionally, for preventing adhesion of organisms to these in-waterstructures, a measure of applying an antifouling paint on surfaces of anin-water structure has been taken.

As the above antifouling paint, an antifouling paint containing ahydrolyzable resin having a hydrolyzable group such as ametal-atom-containing group in a resin side chain as a binder resin(vehicle) is recently used because in such an antifouling paint, theantifouling film surface is gradually self-polished by hydrolysis bybeing dipped in water, and as a result, an antifouling effect can beexerted for a long period of time [for example, Patent Literature 1(Japanese Patent Laying-Open No. 62-57464), Patent Literature 2(Japanese Patent Laying-Open No. 10-298455) and Patent Literature 3(Japanese Patent Laying-Open No. 2001-342432)]. However, in theconventional antifouling paint, it is necessary to separately blend alarge amount of antifouling agent for exerting an antifouling effect fora long period of time.

In order to solve these problems, for example, in Patent Literature 4(Japanese Patent Laying-Open No. 2004-300410) and Patent Literature 5(Japanese Patent Laying-Open No. 2004-307816) there are proposedantifouling coating compositions containing, as a vehicle, a copolymercontaining a polymerizable monomer unit containing (meth)acryl-modifiedsilicon at one terminal and/or both terminals and ametal-atom-containing polymerizable monomer unit containing a divalentmetal atom. However, coating films formed from the antifouling coatingcompositions described in Patent Literature 4 and Patent Literature 5are insufficient in crack resistance, and the coating films can becracked by being dipped in water (sea water or the like) for a longperiod of time, or under an environment where drying and wetting arerepeated, although they exhibit an excellent antifouling property.

CITATION LIST Patent Literature PTL 1: Japanese Patent Laying-Open No.62-57464 PTL 2: Japanese Patent Laying-Open No. 10-298455 PTL 3:Japanese Patent Laying-Open No. 2001-342432 PTL 4: Japanese PatentLaying-Open No. 2004-300410 PTL 5: Japanese Patent Laying-Open No.2004-307816 SUMMARY OF INVENTION Technical Problem

It is an object of the present invention to provide an antifoulingcoating composition capable of forming a coating film that exhibits anexcellent antifouling property over a long period of time and isexcellent in crack resistance even when no antifouling agent iscontained or the blending amount thereof is small. Another object of thepresent invention is to provide an antifouling film formed from theantifouling coating composition, a composite film having the antifoulingfilm, and an in-water structure such as a ship having the antifoulingfilm or the composite film.

Solution to Problem

According to the present invention, there is provided an antifoulingcoating composition containing a hydrolyzable resin having at least onekind of silicon-containing group selected from the group consisting ofthe groups represented by the following general formulas (I), (II),(III) and (IV) and a metal-atom-containing group containing a divalentmetal atom M, and a thermoplastic resin and/or a plasticizer. whereinthe total content of the thermoplastic resin and/or plasticizer is 3 to100 parts by mass per 100 parts by mass of the hydrolyzable resin.

Here, in the general formula (1), a and b each independently representan integer of 2 to 5, m represents an integer of 0 to 50, and nrepresents an integer of 3 to 80. R¹ to R⁵ each independently representan alkyl group, an alkoxy group, a phenyl group, a substituted phenylgroup, a phenoxy group or a substituted phenoxy group.

Here, in the general formula (II), c and d each independently representan integer of 2 to 5, and p represents an integer of 0 to 50, R⁶, R⁷ andR⁸ each independently represent an alkyl group, R^(a) or R^(b).

R^(a) is

(wherein x represents an integer of 0 to 20; and R²³ to R²⁷ are the sameor different and each represent an alkyl group), and

R^(b) is

(wherein y represents an integer of 1 to 20; and R²⁸ and R²⁹ are thesame or different and each represent an alkyl group).

Here, in the general formula (III), e, f, g and h each independentlyrepresent an integer of 2 to 5, q and s each independently represent aninteger of 0 to 50, and r represents an integer of 3 to 80. R⁹ to R¹²each independently represent an alkyl group, an alkoxy group, a phenylgroup, a substituted phenyl group, a phenoxy group or a substitutedphenoxy group.

Here, in the general formula (IV), i, j, k and l each independentlyrepresent an integer of 2 to 5, t and u each independently represent aninteger of 0 to 50, and v and w each independently represent an integerof 0 to 20. R¹³ to R²² are the same or different and each represent analkyl group.

The metal-atom-containing group of the hydrolyzable resin is preferablyat least one kind of group selected from the group consisting of thegroups represented by the following general formulas (V) and (VI).

Here, in the general formula (V), M represents a divalent metal atom,and R³⁰ represents an organic acid residue or an alcohol residue.

Here, in the general formula (VI), M represents a divalent metal atom.

In the antifouling coating composition of the present invention, thehydrolyzable resin is preferably a resin containing a constituent unitderived from at least one kind of silicon-containing polymerizablemonomer (a) selected from the group consisting of a monomer (a1)represented by the following general formula (I′), a monomer (a2)represented by the following general formula (II′), a monomer (a3)represented by the following general formula (III′) and a monomer (a4)represented by the following general formula (IV′), and a constituentunit derived from a metal-atom-containing polymerizable monomer (b)containing a divalent metal atom M.

Here, in the general formula (I′), R³¹ represents a hydrogen atom or amethyl group, and a, b, m, n and R¹ to R⁵ represent the same meaning asmentioned above.

Here, in the general formula (II′), R³² represents a hydrogen atom or amethyl group, and c, d, p and R⁶ to R⁸ represent the same meaning asmentioned above.

Here, in the general formula (III′), R³³ and R³⁴ represent a hydrogenatom or a methyl group, and e, f, g, h, q, r, s and R⁹ to R¹² representthe same meaning as mentioned above.

Here, in the general formula (IV′), R³⁵ and R³⁶ represent a hydrogenatom or a methyl group, and i, j, k, l, t, u, v, w and R¹³ to R²²represent the same meaning as mentioned above.

Preferably, the metal-atom-containing polymerizable monomer (b)containing a divalent metal atom M includes at least one kind selectedfrom the group consisting of a monomer (b1) represented by the followinggeneral formula (V′) and a monomer (b2) represented by (VI′).

Here, in the general formula (V′). R³⁷ represents a hydrogen atom or amethyl group, and M and R³⁰ represent the same meaning as mentionedabove.

Here, in the general formula (VI′). R³⁸ and R³⁹ represent a hydrogenatom or a methyl group, and M represents the same meaning as mentionedabove.

In the hydrolyzable resin, the ratio between the content of theconstituent unit derived from the silicon-containing polymerizablemonomer (a) and the content of the constituent unit derived from themetal-atom-containing polymerizable monomer (b) containing a divalentmetal atom M is preferably in the range of 30/70 to 90/10 by mass ratio.

The thermoplastic resin is preferably at least one kind selected fromthe group consisting of chlorinated paraffin, polyvinyl ether, rosin anda vinyl chloride-isobutylvinyl ether copolymer.

The plasticizer is preferably at least one kind selected from the groupconsisting of a phthalate ester plasticizer and a phosphate esterplasticizer.

The antifouling coating composition of the present invention may contain0 to 20 parts by mass of an antifouling agent per 100 parts by mass ofthe total amount of the hydrolyzable resin, the thermoplastic resin andthe plasticizer.

Also, according to the present invention, there are provided anantifouling film formed from the antifouling coating composition, and acomposite film having the same. The composite film of the presentinvention has a primer film formed from an antirust paint, and anantifouling film formed from the antifouling coating compositionoverlaid on the primer film. The composite film of the present inventionmay further have an intermediate film formed on the entire or part of asurface of the primer film between the primer film and the antifoulingfilm. One preferred example of the intermediate film is a coating filmformed from an antifouling coating composition containing an antifoulingagent.

Further, according to the present invention, an in-water structurehaving the antifouling film or composite film is provided. As apreferred example of the in-water structure, a ship can be recited.

Advantageous Effects of Invention

According to the antifouling coating composition of the presentinvention, even when an antifouling agent is not contained, or theblending amount thereof is small, high antifouling performance can beexerted stably for a long period of time, and an antifouling film thatis excellent in crack resistance can be formed. The antifouling coatingcomposition of the present invention can be suitably used as anantifouling paint for preventing surfaces or inner surfaces of in-waterstructures such as ships; fish nets typically for farming and otherfishing equipment; harbor facilities; oilfences; intake equipment of anelectric generation plant or the like; piping such as water conduits forcooling; bridges, buoyage: industrial water system facilities; andsubmarine bases.

DESCRIPTION OF EMBODIMENTS <Antifouling Coating Composition>

The antifouling coating composition of the present invention contains,as a vehicle ingredient, a hydrolyzable resin (i) having a specificsilicon-containing group as will be described later and ametal-atom-containing group containing a divalent metal atom M[hereinafter, referred to simply as a hydrolyzable resin (i)], and athermoplastic resin and/or a plasticizer (ii). The total content of thethermoplastic resin and/or plasticizer (ii) is within the range of 3 to100 parts by mass per 100 parts by mass of the hydrolyzable resin (i).According to the antifouling coating composition of the presentinvention, it is possible to form an antifouling film that is hydrolyzedat an appropriate speed over a long period of time (particularly, thisproperty is also called a self-polishing property), and hence, it ispossible to obtain an antifouling film that exerts high antifoulingperformance stably for a long period of time (excellent in long-termantifouling property) and is excellent in crack resistance. When theantifouling coating composition is applied to a ship or the like, forexample, the antifouling film is to be dipped in water (sea water or thelike) for a long period of time, and repeatedly exposed to the cycle ofbeing dipped in water for a certain term and then landed, and hence theantifouling film is requested to have such flexibility that is durableto such a condition. According to the antifouling coating composition ofthe present invention, it is possible to form an antifouling film thatis less likely to be cracked even by dipping in water for a long periodof time or by repeated cycles as mentioned above. In the following, theantifouling coating composition of the present invention will bespecifically described.

[Hydrolyzable Resin (i)]

The hydrolyzable resin (i) contained in the antifouling coatingcomposition of the present invention has at least one kind ofsilicon-containing group selected from the group consisting of a grouprepresented by the following general formula (I):

-   -   a group represented by the following general formula (II):

-   -   a group represented by the following general formula (III):

-   -   a group represented by the following general formula (IV):

-   -   and at least one kind of metal-atom-containing group containing        a divalent metal atom M. The hydrolyzable resin (i) having such        a specific silicon-containing group and a metal-atom-containing        group exhibits the property of gradually hydrolyzing in water        (particularly in sea water) due to the hydrolyzability of the        metal-atom-containing group. Therefore, when the antifouling        film formed from the antifouling coating composition containing        the hydrolyzable resin (i) as a vehicle is dipped in water, its        surface is self-polished, and as a result, the coating film        surface is renewed, so that organisms are difficult to adhere        even when an antifouling agent is not contained, and antifouling        performance is exhibited until the coating film is completely        exhausted.

In the general formula (I), a and b each independently represent aninteger of 2 to 5, m represents an integer of 0 to 50, and n representsan integer of 3 to 80. R¹ to R⁵ each independently represent an alkylgroup, an alkoxy group, a phenyl group, a substituted phenyl group, aphenoxy group or a substituted phenoxy group.

In the general formula (II), c and d each independently represent aninteger of 2 to 5, and p represents an integer of 0 to 50. R⁶, R⁷ and R⁸each independently represent an alkyl group, R^(a) or R^(b), R^(a) is

(wherein x represents an integer of 0 to 20; and R²³ to R²⁷ are the sameor different and each represent an alkyl group), and R^(b) is

(wherein y represents an integer of 1 to 20; and R²⁸ and R²⁹ are thesame or different and each represent an alkyl group).

In the general formula (III), e, f, g and h each independently representan integer of 2 to 5, q and s each independently represent an integer of0 to 50, and r represents an integer of 3 to 80. R⁹ to R¹² eachindependently represent an alkyl group, an alkoxy group, a phenyl group,a substituted phenyl group, a phenoxy group or a substituted phenoxygroup.

In the general formula (IV), i, j, k and l each independently representan integer of 2 to 5, t and u each independently represent an integer of0 to 50, and v and w each independently represent an integer of 0 to 20.R¹³ to R²² are the same or different and each represent an alkyl group.

The hydrolyzable resin (i) may have two or more kinds ofsilicon-containing groups selected from the group consisting of thegroups represented by the general formulas (I), (II), (III) and (IV). Inthis case, the hydrolyzable resin (i) may have two or more kinds of thegroups represented by the general formula (I), two or more kinds of thegroups represented by the general formula (II), two or more kinds of thegroups represented by the general formula (III), and/or two or morekinds of the groups represented by the general formula (IV).

Since the metal-atom-containing group containing a divalent metal atom Mis able to keep the self-polishing property of the coating film stablyfor a long period of time, and thus allows formation of a coating filmthat is excellent in long-term antifouling property and excellent incrack resistance and adherence with a base, it is preferably at leastone kind of group selected from the group consisting of a grouprepresented by the following general formula (V):

-   -   and a group represented by he following general formula (VI):

In the general formulas (V) and (VI). M represents a divalent metalatom, and R³⁰ represents an organic acid residue or an alcohol residue.The hydrolyzable resin (i) may have both the general formulas (V) and(VI). As the divalent metal atom M, for example, Mg. Zn and Cu can berecited, and Zn or Cu is preferred.

While the hydrolyzable resin (i) is not particularly limited insofar asit has a silicon-containing group and a metal-atom-containing group asmentioned above, an acrylic resin containing a constituent unit derivedfrom at least one kind of the silicon-containing polymerizable monomer(a) selected from the group consisting of a monomer (a1) represented bythe following general formula (F), a monomer (a2) represented by thefollowing general formula (II′), a monomer (a3) represented by thefollowing general formula (III′) and a monomer (a4) represented by thefollowing general formula (IV′) and a constituent unit derived from themetal-atom-containing polymerizable monomer (b) containing a divalentmetal atom M may be suitably used.

Here, in the general formula (I′), R³¹ represents a hydrogen atom or amethyl group, and a, b, m, n and R¹ to R⁵ represent the same meaning asmentioned above.

Here, in the general formula (II′), R³² represents a hydrogen atom or amethyl group, and c, d, p and R⁶ to R⁸ represent the same meaning asmentioned above.

Here, in the general formula (III′), R³³ and R³⁴ represent a hydrogenatom or a methyl group, and e, f, g, h, q, r, s and R⁹ to R¹² representthe same meaning as mentioned above.

Here, in the general formula (IV′), R³⁵ and R³⁶ represent a hydrogenatom or a methyl group, and i, j, k, l, t, u, v, w and R¹³ to R²²represent the same meaning as mentioned above.

The monomer (a1) represented by the general formula (I′), the monomer(a2) represented by the general formula (II′), the monomer (a3)represented by the general formula (III′) and the monomer (a4)represented by the general formula (IV′) are respectivelysilicon-containing polymerizable monomers having silicon-containinggroups represented by the general formulas (I), (II), (III) and (IV).

Since the metal-atom-containing polymerizable monomer (b) containing adivalent metal atom M as mentioned above is able to keep theself-polishing property of a coating film stably for a long period oftime, and thus is able to form a coating film having an excellentlong-term antifouling property, and excellent crack resistance andadherence with a base, it preferably contains at least one kind selectedfrom the group consisting of the monomer (b 1) represented by thefollowing general formula (V′) and the monomer (b2) represented by(VI′).

Here, in the general formula (V′), R³⁷ represents a hydrogen atom or amethyl group, and M and R³⁰ represent the same meaning as mentionedabove.

Here, in the general formula (VI′), R³⁸ and R³⁹ represent a hydrogenatom or a methyl group, and M represents the same meaning as mentionedabove.

The monomer (b1) represented by the general formula (V′) and the monomer(b2) represented by the general formula (VI′) are respectivelymetal-atom-containing polymerizable monomers havingmetal-atom-containing groups represented by the general formulas (V) and(VI).

[1] Silicon-Containing Polymerizable Monomer (a)

The silicon-containing polymerizable monomer (a1) that can form thehydrolyzable resin (i) is represented by the general formula (I′), andin the formula, a and b each independently represent an integer of 2 to5, m represents an integer of 0 to 50, and n represents an integer of 3to 80. R¹ to R⁵ each independently represent an alkyl group, an alkoxygroup, a phenyl group, a substituted phenyl group, a phenoxy group or asubstituted phenoxy group, and R³¹ represents a hydrogen atom or amethyl group. By using the silicon-containing polymerizable monomer (a1)as the silicon-containing polymerizable monomer (a), the hydrolyzableresin (i) which is an acrylic resin having a silicon-containing grouprepresented by the general formula (I) in a side chain is obtained.

In the general formula (I′) (ditto with the general formula (I), dittowith the following), m represents the average polymerization degree of apolyether structure, and may be 0, but is preferably more than 0 becausethere is a tendency that the recoating property with an old coating filmis excellent. Further, m is preferably 50 or less because the waterresistance of the coating film tends to be excellent, and is preferably30 or less because the recoating property with an old coating film tendsto be excellent. m is more preferably in the range of 3 to 25, and isfurther preferably in the range of 5 to 20.

In the general formula (F), a is preferably 2 or 3, and the one whereina is 2 and the one wherein a is 3 may be used together, b is preferably2 or 3.

In the general formula (I′), n represents the average polymerizationdegree of a silicon-containing structure, and is an integer in the rangeof 3 to 80. By setting n to 3 or larger, it is possible to develop ahigher antifouling effect. Also by setting n to 80 or less, excellentcompatibility with other polymerizable monomers is exhibited, andsolubility in a general organic solvent of the obtained hydrolyzableresin (i) can be improved. n is preferably in the range of 5 to 50, andis more preferably in the range of 8 to 40.

In the general formula (I′), R¹ to R⁵ are preferably an alkyl grouphaving 1 to 18 carbon atoms, more preferably a methyl group or an ethylgroup, and further preferably a methyl group.

Concrete examples of the silicon-containing polymerizable monomer (a1)represented by the general formula (I′) include “FM-0711”, “FM-0721”,and “FM-0725” (trade names) which are products of CHISSO CORPORATION,and “X-24-8201”, “X-22-174DX”, and “X-22-2426” (trade names) which areproducts of Shin-Etsu Chemical Co., Ltd. as those wherein m is 0. Asthose wherein m is more than 0, “F2-254-04” and “F2-254-14” (tradenames) which are products of Nippon Unicar Company Limited and so on arerecited. While products of Nippon Unicar Company Limited as the concreteexamples of the silicon-containing polymerizable monomer (a1) aredescribed by their trade names, silicone business in Nippon UnicarCompany Limited was assigned to Dow Corning Toray Co., Ltd. in 2004, andcorresponding products are now available from the assignee. This alsoapplies to the products of Nippon Unicar Company Limited as will bedescribed below.

The hydrolyzable resin (i) may contain two or more kinds of constituentunits derived from the silicon-containing polymerizable monomer (a1)) asthe silicon-containing polymerizable monomer (a).

The silicon-containing polymerizable monomer (a2) that can form thehydrolyzable resin (i) is represented by the general formula (II′), andin the formula, c and d each independently represent an integer of 2 to5, and p represents an integer of 0 to 50. R⁶, R⁷ and R⁸ eachindependently represent an alkyl group. R^(a) or R^(b), and R³²represents a hydrogen atom or a methyl group. R^(a) and R^(b) are asdescribed above. By using the silicon-containing polymerizable monomer(a2) as the silicon-containing polymerizable monomer (a), thehydrolyzable resin (i) which is an acrylic resin having asilicon-containing group represented by the general formula (II) in aside chain is obtained.

In the general formula (II′) (ditto with the general formula (II), dittowith the following), p represents the average polymerization degree of apolyether structure, and may be 0, but is preferably more than 0 becausethere is a tendency that the recoating property with an old coating filmis excellent. Further, p is preferably 50 or less because the waterresistance of the coating film tends to be excellent, and is preferably30 or less because the recoating property with an old coating film tendsto be excellent. p is more preferably in the range of 3 to 25, and isfurther preferably in the range of 5 to 20.

In the general formula (II′), c is preferably 2 or 3, and the onewherein c is 2 and the one wherein c is 3 may be used together. d ispreferably 2 or 3.

In the general formula (II′), x and y each represent the averagepolymerization degree of a silicon-containing structure or a polyetherstructure introduced into a side chain, and is an integer in the rangeof 0 to 20 and an integer in the range of 1 to 20, respectively. Bysetting x and y to 20 or less, excellent compatibility with otherpolymerizable monomers is exhibited, and solubility of the obtainedhydrolyzable resin (i) in a general organic solvent can be improved. xand y are preferably in the range of 10 or less, and more preferably inthe range of 5 or less.

In the general formula (II′), as an alkyl group that can he selected inR⁶ to R⁸ and R²³ to R²⁹, for example, a methyl group, an ethyl group, an-propyl group, a n-butyl group and the like are recited. A methyl groupor an ethyl group are preferred, and a methyl group is more preferred.

Concrete examples of the silicon-containing polymerizable monomer (a2)represented by the general formula (II′) include “TM-0701” (trade name)which is a product of CHISSO CORPORATION, “X-22-2404” (trade name) whichis a product of Shin-Etsu Chemical Co., Ltd., and “F2-250-01” and“F2-302-01” (trade names) which are products of Nippon Unicar CompanyLimited as those wherein p is 0. As those wherein p is more than 0,“F2-302-04” (trade name) which is a product of Nippon Unicar CompanyLimited and so on are recited.

The hydrolyzable resin (i) may contain two or more kinds of constituentunits derived from the silicon-containing polymerizable monomer (a2) asthe silicon-containing polymerizable monomer (a).

The silicon-containing polymerizable monomer (a3) that can form thehydrolyzable resin (i) is represented by the general formula (III′), andin the formula, e, f, g and h each independently represent an integer of2 to 5, q and s each independently represent an integer of 0 to 50, andr represents an integer of 3 to 80. R⁹ to R¹² each independentlyrepresent an alkyl group, an alkoxy group, a phenyl group, a substitutedphenyl group, a phenoxy group or a substituted phenoxy group, and R³³and R³⁴ represent a hydrogen atom or a methyl group. By using thesilicon-containing polymerizable monomer (a3) as the silicon-containingpolymerizable monomer (a), the hydrolyzable resin (i) which is anacrylic resin having a silicon-containing group represented by thegeneral formula (III) (This silicon-containing group is a cross-linkinggroup that cross-links polymer main chains,) is obtained.

In the general formula (III′) (ditto with the general formula (III),ditto with the following), q and s represent the average polymerizationdegree of a polyether structure, and may he 0. but are preferably morethan 0 because there is a tendency that the recoating property with anold coating film is excellent. Further, q and s are preferably 50 orless because the water resistance of the coating film tends to beexcellent, and are preferably 30 or less because the recoating propertywith an old coating film tends to be excellent. q and s are morepreferably in the range of 3 to 25, and are further preferably in therange of 5 to 20.

In the general formula (III′), e and h are preferably 2 or 3. and thosewherein e and h are 2 and 3 may be used together, f and g are preferably2 or 3.

In the general formula (III′), r represents the average polymerizationdegree of a silicon-containing structure, and is an integer in the rangeof 3 to 80. By setting r to 3 or larger, it is possible to develop ahigher antifouling effect. Also by setting r to 80 or less, excellentcompatibility with other polymerizable monomers is exhibited, andsolubility in a general organic solvent of the obtained hydrolyzableresin (i) can be improved. r is preferably in the range of 5 to 50, andis more preferably in the range of 8 to 40.

In the general formula (III′). R⁹ to R¹² are preferably an alkyl grouphaving 1 to 18 carbon atoms, more preferably a methyl group or an ethylgroup, and further preferably a methyl group.

Concrete examples of the silicon-containing polymerizable monomer (a3)represented by the general formula (III′) include “FM-7711”, “FM-7721”,and “FM-7725” (trade names) which are products of CHISSO CORPORATION,and “F2-311-02” (trade name) which is a product of Nippon Unicar CompanyLimited as those wherein q and s are 0. As those wherein q and s aremore than 0, “F2-354-04” (trade name) which is a product of NipponUnicar Company Limited and so on are recited.

The hydrolyzable resin (i) may contain two or more kinds of constituentunits derived from the silicon-containing polymerizable monomer (a3) asthe silicon-containing polymerizable monomer (a).

The silicon-containing polymerizable monomer (a4) that can form thehydrolyzable resin (i) is represented by the general formula (IV′), andin the formula, i, j, k and l each independently represent an integer of2 to 5, t and u each independently represent an integer of 0 to 50, andv and w each independently represent an integer of 0 to 20. R¹³ to R²²are the same or different and each represent an alkyl group, and R³⁵ andR³⁶ represent a hydrogen atom or a methyl group. By using thesilicon-containing polymerizable monomer (a4) as the silicon-containingpolymerizable monomer (a), the hydrolyzable resin (i) which is anacrylic resin having a silicon-containing group represented by thegeneral formula (IV) (This silicon-containing group is a cross-linkinggroup that cross-links polymer main chains.) is obtained.

In the general formula (IV′) (ditto with the general formula (IV), dittowith the following), t and u each represent the average polymerizationdegree of a polyether structure, and may be 0, but is preferably morethan 0 because there is a tendency that the recoating property with anold coating film is excellent. Further, t and u are preferably 50 orless because the water resistance of the coating film tends to beexcellent, and are preferably 30 or less because the recoating propertywith an old coating film tends to be excellent. t and u are morepreferably in the range of 3 to 25, and are further preferably in therange of 5 to 20.

In the general formula (IV′), i and 1 are preferably 2 or 3, and thosewherein i and 1 are 2 and 3 may be used together. j and k are preferably2 or 3.

In the general formula (IV′), v and w each represent the averagepolymerization degree of a silicon-containing structure introduced intoa side chain, and are an integer in the range of 0 to 20. By setting vand w to 20 or less, excellent compatibility with other polymerizablemonomers is exhibited, and solubility of the obtained hydrolyzable resin(i) in a general organic solvent can be improved. v and w are preferablyin the range of 10 or less, and more preferably in the range of 5 orless.

In the general formula (IV′), as an alkyl group that can be selected inR¹³ to R²², for example, a methyl group, an ethyl group, a n-propylgroup, a n-butyl group and the like are recited. A methyl group or anethyl group are preferred, and a methyl group is more preferred.

Concrete examples of the silicon-containing polymerizable monomer (a4)represented by the general formula (IV′) include “F2-312-01” (tradename) which is a product of Nippon Unicar Company Limited. for example.as those wherein t and u are 0. As those wherein t and u are more than0, “F2-312-04” (trade name) which is a product of Nippon Unicar CompanyLimited and so on are recited.

The hydrolyzable resin (i) may contain two or more kinds of constituentunits derived from the silicon-containing polymerizable monomer (a4) asthe silicon-containing polymerizable monomer (a).

The hydrolyzable resin (i) may contain constituent units derived fromtwo or more kinds of silicon-containing polymerizable monomers selectedfrom the silicon-containing polymerizable monomers (a1), (a2), (a3) and(a4). Among these, as one preferred embodiment. a form using both apolymerizable monomer containing (meth)acryl-modified silicon at oneterminal [silicon-containing polymerizable monomer (a1) and/or (a2)] anda polymerizable monomer containing (meth)acryl-modified silicon at bothterminals [silicon-containing polymerizable monomer (a3) and/or (a4)]can be recited.

Among the entire constituent units forming the hydrolyzable resin (i),the content of the constituent unit derived from the silicon-containingpolymerizable monomer (a) is preferably 1 to 60% by mass, morepreferably 5 to 50% by mass, and further preferably 10 to 40% by mass.With the content of I% by mass or more, an antifouling effect tends toappear even when an antifouling agent is not separately contained, andwith the content of 60% by mass or less, a good balance between along-term antifouling property and adherence with a base tends to beobtained.

Metal-Atom-Containing Polymerizable Monomer (b)

The metal-atom-containing polymerizable monomer (b) is a monomer forintroducing a metal-atom-containing group containing a divalent metalatom M into the hydrolyzable resin (i). Without a metal-atom-containinggroup, the hydrolyzability of the obtained resin is insufficient so thatan excellent self-polishing property of a coating film is not obtained,and it is difficult to obtain a coating film exhibiting an excellentantifouling property. Without a metal-atom-containing group, adherencewith a base and crack resistance of a coating film tend to be defective.As the divalent metal atom M, Mg, Zn, Cu and so on can be recited, andZn or Cu is preferable.

The metal-atom-containing polymerizable monomer (b1)) that can form thehydrolyzable resin (i) is represented by the general formula (V′), andin the formula. R³⁷ represents a hydrogen atom or a methyl group. Mrepresents a divalent metal atom, and R³⁰ represents an organic acidresidue or an alcohol residue. By using the metal-atom-containingpolymerizable monomer (b1) as the metal-atom-containing polymerizablemonomer (b), the hydrolyzable resin (i) which is an acrylic resin havinga metal-atom-containing group represented by the general formula (V) isobtained.

In R³⁰, as an organic acid forming an organic acid residue, for example,monobasic organic acids such as acetic acid, monochloroacetic acid,monofluoroacetic acid, propionic acid, caproic acid. caprylic acid,2-ethylhexyl acid, capric acid, versatic acid, isostearic acid, palmiticacid, cresotinic acid, oleic acid, elaidic acid, linoleic acid,linolenic acid, stearolic acid, ricinoleic acid, ricinoelaidic acid,brassidic acid, erucic acid, α-naphthoic acid, β-naphthoic acid, benzoicacid, 2,4,5-trichlorophenoxyacetic acid. 2,4-dichlorophenoxyacetic acid,quinoline carboxylic acid, nitrobenzoic acid, nitronaphthalenecarboxylicacid, and pyruvic acid are recited. Among these, using the one having afatty acid organic acid residue is preferred because a coating filmwithout cracking and peeling tends to be kept for a long period of time.In particular, zinc oleate (meth)acrylate or zinc versatate(meth)acrylate having high flexibility is preferably used as themetal-atom-containing polymerizable monomer (b1).

As other preferred organic acids, monobasic cyclic organic acids otherthan aromatic organic acids can be recited. As monobasic cyclic organicacids, for example, those having a cycloalkyl group such as naphthenicacid, and resin acids such as tricyclic resin acids and salts thereofcan be recited. As a tricyclic resin acid, for example, a monobasic acidhaving a diterpene hydrocarbon backbone can be recited, and as such, forexample, compounds having abietane, pimarane, isopimarane, and labdanebackbones can be recited. More concretely, for example, abietic acid,neoabietic acid, dehydroabietic acid, hydrogenated abietic acid,palustris acid, pimaric acid, isopimaric acid, levopimaric acid,dextropimaric acid, sandaracopimaric acid, and salts thereof arerecited. Among these, abietic acid, hydrogenated abietic acid and saltsthereof are preferred because hydrolysis appropriately occurs, and anexcellent long-term antifouling property and excellent crack resistanceof a coating film are obtained, and the acids are easily available.

The monobasic cyclic organic acid does not have to be highly purified,and. for example, pine resin, resin acid of pine and so on may be used.As such, for example, rosin, hydrogenated rosin, disproportionated rosinand naphthenic acid can be recited. The rosin referred to hereinincludes gum rosin, wood rosin, tall oil rosin and so on. Rosin,hydrogenated rosin and disproportionated rosin are preferred in thatthey are cheap and easily available, and excellent in handleability andexert a long-term antifouling property.

The acid value of the monobasic cyclic organic acid is preferably 100 mgKOH/g or more and 220 mg KOH/g or less, more preferably 120 mg KOH/g ormore and 190 mg KOH/g or less, and further preferably 140 mg KOH/g ormore and 185 mg KOH/g or less. When the one having an acid value withinthe above range is used as a monobasic cyclic organic acid forming R³⁰,the hydrolysis speed of the hydrolyzable resin (i) is appropriate, sothat the self-polishing property of the coating film can be kept stablyfor a long period of time. and thus the antifouling effect can be keptfor a longer term.

An organic acid residue of the metal-atom-containing polymerizablemonomer (b1) may be formed of only one kind of organic acid or two ormore kinds of organic acids.

As a production method of the metal-atom-containing polymerizablemonomer (b1) having an organic acid residue as R³⁰, for example, amethod of reacting an inorganic metal compound, with a carboxylicgroup-containing radical polymerizable monomer such as (meth)acrylicacid, and a nonpolymerizable organic acid (an organic acid forming theorganic acid residue) in an organic solvent containing an alcoholiccompound can be recited. A constituent unit derived from themetal-atom-containing polymerizable monomer (b1) may be formed by amethod of reacting a resin obtainable by polymerization of a monomermixture containing a carboxylic group-containing radical polymerizablemonomer such as (meth)acrylic acid, with a metal compound, and anonpolymerizable organic acid (an organic acid forming the organic acidresidue).

The metal-atom-containing polymerizable monomer (b2) that can form thehydrolyzable resin (i) is represented by the general formula (VI′), andin the formula. R³⁸ and R³⁹ represent a hydrogen atom or a methyl group,and M represents a divalent metal atom. By using themetal-atom-containing polymerizable monomer (b2) as themetal-atom-containing polymerizable monomer (b), the hydrolyzable resin(i) which is an acrylic resin having a metal-atom-containing group (thismetal-atom-containing group is a cross-linking group that cross-linkspolymer main chains) represented by the general formula (VI) isobtained.

Concrete examples of the metal-atom-containing polymerizable monomer(b2) include magnesium acrylate [(CH₂=CHCOO)₂Mg], magnesium methacrylate[(CH₂=C(CH₃)COO)₂Mg], zinc acrylate [(CH₂=CHCOO)₂Zn], zinc methacrylate[(CH₂=C(CH₃)COO)₂Zn], copper acrylate [(CH₂=CHCOO)₂Cu], and coppermethacrylate [(CH₂=C(CH₃)COO)₂Cu]. These may be used alone or incombination of two or more kinds that are appropriately selected asnecessary.

As a production method of the metal-atom-containing polymerizablemonomer (b2), for example, a method of reacting a polymerizableunsaturated organic acid such as (meth)acrylic acid with a metalcompound in an organic solvent containing an alcoholic compound togetherwith water can be recited. In this case. it is preferred to adjust thecontent of water in the reactant within the range of 0.01 to 30% bymass.

The hydrolyzable resin (i) may contain both a constituent unit derivedfrom the metal-atom-containing polymerizable monomer (b1) and aconstituent unit derived from the metal-atom-containing polymerizablemonomer (b2). When both the metal-atom-containing polymerizable monomer(b1) and the metal-atom-containing polymerizable monomer (b2) are usedas monomers forming the hydrolyzable resin (i), the ratio betweencontents of the constituent unit derived from the metal-atom-containingpolymerizable monomer (b1) and the constituent unit derived from themetal-atom-containing polymerizable monomer (b2) in the hydrolyzableresin (i) is preferably in the range of 20/80 to 80/20 (molar ratio),and is more preferably in the range of 30/70 to 70/30 (molar ratio). Byadjusting the ratio of contents within this range, an antifouling filmexerting an excellent antifouling property for a long period of time andhaving excellent crack resistance and adherence with a base tends to beeasily obtained even when no or a small amount of antifouling agent iscontained.

In the entire constituent units forming the hydrolyzable resin (i), thecontent of the constituent unit derived from the metal-atom-containingpolymerizable monomer (b) is preferably 5 to 30% by mass, and morepreferably 10 to 20% by mass. By setting the content to 5% by mass ormore, adherence with a base improves, and the self-polishing property ofa coating film formed therefrom tends to be kept stably for a longerterm, and by setting the content to 30% by mass or less, the effect ofimproving the balance between the long-term self-polishing property, andcrack resistance after dipping in sea water and adherence with a basebecomes more significant, and the long-term self-polishing property iskept, and physical properties of a coating film tend to improve.

In the hydrolyzable resin (i), the ratio between the content of theconstituent unit derived from the silicon-containing polymerizablemonomer (a) and the content of the constituent unit derived from themetal-atom-containing polymerizable monomer (b) is preferably in therange of 30/70 to 90/10 by mass ratio, and is more preferably in therange of 45/55 to 85/15. By setting the ratio to 30/70 or more, anantifouling effect tends to develop even when an antifouling agent isnot separately contained. When the ratio is less than 30/70, flexibilityof a coating film obtained therefrom can be impaired, or theself-polishing property of the coating film can be too high. By settingthe ratio to 90/10 or less, an excellent balance between the long-termantifouling property and adherence with a base tends to be obtained.When the ratio exceeds 90/10, hydrolysis of a coating film obtainedtherefrom can be impaired, so that there is a possibility that theself-polishing property of the coating film is impaired.

Different Monomer Component (c)

The hydrolyzable resin (i) may contain a constituent unit derived from amonomer component (c) other than the silicon-containing polymerizablemonomer (a) and the metal-atom-containing polymerizable monomer (b).

The different monomer component (c) is not particularly limited insofaras it is an unsaturated monomer capable of copolymerizing with thesilicon-containing polymerizable monomer (a) and themetal-atom-containing polymerizable monomer (b), and for example,(meth)acrylic acid ester monomers such as methyl (meth)acrylate, ethyl(meth)acrylate. 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl(meth)acrylate, phenoxyethyl (meth)acrylate, 2-(2-ethylhexaoxy)ethyl(meth)acrylate, 1-methyl-2-methoxyethyl (meth)acrylate, 3-methoxybutyl(meth)acrylate, 3-methyl-3-methoxybutyl (meth)acrylate, m-methoxyphenyl(meth)acrylate, p-methoxyphenyl (meth)acrylate, o-methoxyphenylethyl(meth)acrylate, m-methoxyphenylethyl (meth)acrylate,p-methoxyphenylethyl (meth)acrylate. n-propyl (meth)acrylate, i-propyl(meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl(meth)acrylate. 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate,stearyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate,isobornyl (meth)acrylate, cyclohexyl (meth)acrylate and glycidyl(meth)acrylate; hydroxy group-containing monomers such as 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl(meth)acrylate, 2-hydroxybutyl (meth)acrylate and 4-hydroxybutyl(meth)acrylate; adducts of 2-hydroxyethyl(meth)acrylate, with ethyleneoxide, propylene oxide, γ-butyrolactone, ε-caprolactone or the like;dimers or trimers such as 2-hydroxyethyl (meth)acrylate and2-hydroxypropyl (meth)acrylate; monomers having plural hydroxy groupssuch as glycerol (meth)acrylate; primary and secondary aminogroup-containing vinyl monomers such as butylaminoethyl (meth)acrylateand (meth)acrylamide; tertiary amino group-containing vinyl monomerssuch as dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, dimethylaminobutyl(meth)acrylate, dibutylaminoethyl (meth)acrylate, dimethylaminoethyl(meth)acrylamide and dimethylaminopropyl (meth)acrylamide: heterocyclicbasic monomers such as vinyl pyrrolidone, vinyl pyridine and vinylcarbazole: and vinyl monomers such as styrene, vinyltoluene,α-methylstyrene, (meth)acrylonitrile, vinyl acetate and vinyl propionatecan be recited.

The content of the constituent unit derived from the different monomercomponent (c) in the entire constituent units forming the hydrolyzableresin (i) is preferably 0.1 to 89% by mass, more preferably 7 to 75% bymass, and further preferably 10 to 70% by mass. By setting the contentto 0.1% by mass or more, it becomes possible to regulate the balance ofvarious characteristics of the antifouling coating composition obtainedtherefrom, and by setting the content to 89% by mass or less, thecoating film formed therefrom is provided with excellent hydrolyzabilityfor a long period of time, and an excellent antifouling property appearseven when an antifouling agent is not used, and the balance withadherence of the coating film with respect to a base tends to beexcellent.

The production method of the hydrolyzable resin (i) is not particularlylimited, and for example, a method of reacting a monomer mixture of theaforementioned monomers in the presence of a radical initiator at areaction temperature of 60 to 180° C. for 5 to 14 hours. As the radicalinitiator, for example, 2,2-azobisisobutyronitrile,2,2-azobis(2,4-dimethylvaleronitrile),2,2-azobis(2-methylbutyronitrile), benzoyl peroxide, cumenehydroperoxide, lauryl peroxide, di-t-butylperoxide,t-butylperoxy-2-ethylhexanoate and the like are recited. As apolymerization method, an emulsion polymerization method, a suspensionpolymerization method and the like can be employed in addition to asolution polymerization method carried out in an organic solvent,however, a solution polymerization method using a general organicsolvent such as toluene, xylene, methyl isobutyl ketone, or n-butylacetate is advantageous from the view point of productivity andperformance of the hydrolyzable resin (i).

Also, when the metal-atom-containing polymerizable monomer (b2) is used,it is preferred to use a chain transfer agent to make the antifoulingcoating composition highly solid, to improve the productivity and toprevent generation of cullet at the time of polymerization. As the chaintransfer agent, a chain transfer agent other than mercaptan, such as astyrene dimer is preferred from the view point of compatibility with themetal-atom-containing polymerizable monomer (h).

The weight average molecular weight of the hydrolyzable resin (i) isgenerally within the range of 1000 to 3000000, preferably within therange of 3000 to 100000, and more preferably within the range of 5000 to50000, although it differs depending on the polymerization condition.When the weight average molecular weight is 1000 or more, an antifoulingproperty tends to appear when a coating film is formed, and when theweight average molecular weight is 3000000 or less, the hydrolyzableresin (i) tends to be dispersed uniformly in the coating composition.The weight average molecular weight referred to herein means the weightaverage molecular weight in terms of polystyrene measured by gelpermeation chromatography (GPC).

The fact that the hydrolyzable resin (i) is a resin containing one ormore kinds of silicon-containing groups represented by the generalformulas (I) to (IV) (a resin containing a constituent unit derived fromone or more kinds of the silicon-containing polymerizable monomers (a1)to (a4)) can be confirmed by using, for example, ¹H-NMR, ICP emissionspectrometry. The fact that the hydrolyzable resin (i) is a resincontaining one or more kinds of the metal-atom-containing groupsrepresented by the general formulas (V) to (VI) (a resin containing aconstituent unit derived from one or more kinds of themetal-atom-containing polymerizable monomers (b1) to (b2)) can beconfirmed, for example, by using atomic absorption spectrometry.

In the antifouling coating composition of the present invention. thecontent of the hydrolyzable resin (i) is preferably 30 to 97% by mass insolids contained in the antifouling coating composition. When thecontent is less than 30% by mass, adherence of the coating film withrespect to a base deteriorates, and an antifouling effect tends not tobe sufficiently exerted. When the content is more than 97% by mass,crack resistance of the coating film tends to deteriorate. Solidscontained in an antifouling coating composition refers to the sum of theingredients other than a solvent contained in the antifouling coatingcomposition.

[Thermoplastic Resin and/or Plasticizer (ii)]

The antifouling coating composition of the present invention containsthe thermoplastic resin and/or plasticizer (ii) together with thehydrolyzable resin (i). By adding the thermoplastic resin and/orplasticizer (ii), crack resistance of a coating film can be improved.Since it becomes possible to control the polishing rate (polishingspeed) of the coating film to an appropriate speed, it is advantageousalso in the point of the long-term antifouling property of the coatingfilm.

As the thermoplastic resin, for example, chlorinated paraffin;chlorinated polyolefins such as chlorinated rubber, chlorinatedpolyethylene and chlorinated polypropylene; polyvinyl ether;polypropylene sebacate; partially hydrogenated terphenyl; polyvinylacetate; poly(meth)acrylic acid alkyl esters such as methyl(meth)acrylate copolymers. ethyl (meth)acrylate copolymers, propyl(meth)acrylate copolymers, butyl (meth)acrylate copolymers andcyclohexyl (meth)acrylate copolymers; polyether polyols; alkyd resins;polyester resins; vinyl chloride resins such as a vinyl chloride-vinylacetate copolymer, a vinyl chloride-vinyl propionate copolymer. a vinylchloride-isobutyl vinyl ether copolymer, a vinyl chloride-isopropylvinyl ether copolymer and a vinyl chloride-ethyl vinyl ether copolymer;silicon oil; fats and oils and purified substances thereof; vaseline;liquid paraffin; rosin, hydrogenated rosin, naphthenic acid, fatty acidsand divalent metal salts thereof; and so on can be recited. Examples ofthe fats and oils and purified substances thereof include fats and oilsthat are solid at normal temperature, such as, for example, wax(including animal-derived wax such as bees wax, plant-derived wax and soon) and fats and oils that are liquid at normal temperature such ascastor oil. These thermoplastic resins may be used alone or incombination of two or more kinds.

Among the above, chlorinated paraffin, polyvinyl ether, polyetherpolyols, rosin, and a vinyl chloride-isobutyl vinyl ether copolymer areparticularly preferred, and in particular, chlorinated paraffin,polyvinyl ether, rosin and a vinyl chloride-isobutyl vinyl ethercopolymer can be more preferably used because they are suited foradjusting plasticity of a coating film and an exhausted amount of acoating film.

As the plasticizer, for example, phthalate ester plasticizers such asdioctyl phthalate (DOP), dimethyl phthalate, dicyclohexyl phthalate anddiisodecyl phthalate (MP): aliphatic dibasic acid ester plasticizerssuch as isohutyl adipate and dibutyl sebacate: glycol ester plasticizerssuch as diethyleneglycol dibenzoate and pentaerythritol alkyl ester;phosphate ester plasticizers such as tricresyl phosphoric acid(tricresyl phosphate), triaryl phosphoric acid (triaryl phosphate) andtrichloroethyl phosphoric acid: epoxy plasticizers such as epoxy soybeanoil and octyl epoxystearate: organotin plasticizers such as dioctyl tinlaurate and dibutyl tin laurate; trioctyl trimellitate, triacetylene andthe like can be recited. These plasticizers may be used alone or incombination of two or more kinds.

Among these, phthalate ester plasticizers such as dioctyl phthalate(DOP), dimethyl phthalate, dicyclohexyl phthalate and diisodecylphthalate (DIDP), and phosphate ester plasticizers such as tricresylphosphoric acid (tricresyl phosphate), triaryl phosphoric acid (triarylphosphate) and trichloroethyl phosphoric acid are particularly excellentin compatibility with the hydrolyzable resin and the thermoplasticresin, and are able to improve crack resistance unifoinily over theentire coating film, and hence can be preferably used.

The antifouling coating composition of the present invention may containonly a thermoplastic resin, or only a plasticizer, or contain both of athermoplastic resin and a plasticizer. Using both a thermoplastic resinand a plasticizer is preferred because a coating film having excellenttoughness and plasticity is obtained.

The total content of the thermoplastic resin and/or plasticizer (ii) iswithin the range of 3 to 100 parts by mass, and preferably 5 to 50 partsby mass per 100 parts by mass of the hydrolyzable resin (i). When thetotal content of the thermoplastic resin and/or plasticizer (ii) is lessthan 3 parts by mass per 100 parts by mass of the hydrolyzable resin(i), the effect of improving the crack resistance by addition of thethermoplastic resin and/or plasticizer (ii) tends not to be recognized,and when the content of the thermoplastic resin and/or plasticizer (ii)is extremely small or the thermoplastic resin and/or plasticizer (ii) isnot contained, an appropriate polishing rate (polishing speed) is notobtained, and a long-term antifouling property may not be imparted.Further, when the total content of the thermoplastic resin and/orplasticizer (ii) exceeds 100 parts by mass per 100 parts by mass of thehydrolyzable resin (i), adherence of the coating film with a basedeteriorates, and the antifouling property tends to deteriorate.

[Antifouling Agent]

While an antifouling film obtained from the antifouling coatingcomposition of the present invention exerts excellent antifoulingperformance owing to the antifouling effect based on the self-polishingproperty exhibited by the hydrolyzable resin (i), the antifoulingcoating composition may be mixed with an antifouling agent as necessaryfor further improving the antifouling performance or further improvinglong-term continuity of the antifouling property. As the antifoulingagent, those known in the art may be used without particular limitation,and for example, inorganic compounds, organic compounds containing ametal and organic compounds not containing a metal can be recited.

Concrete examples of the antifouling agent include metal salts such aszinc oxide; cuprous oxide; manganese ethylene-bis-dithiocarbamate; zincdimethyldithiocarbamate;2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine;2,4,5.6-tetrachloroisophthalonitrile; N,N-dimethyldichlorophenyl urea;zinc ethylene-bis-dithiocarbamate; rhodan copper (cuprous thiocyanate);4,5-dichloro-2-n-octyl-4-isothiazoline-3-on(4,5,-dichloro-2-n-octyl-3(2H)isothiazolone);N-(fluorodichloromethylthio)phthalimide;N,N′-dimethyl-N′-phenyl-(N-fluorodichloromethylthio)sulfamide;2-pyridinethiol-1-oxide zinc salt (zinc pyrithione) and copper salt(copper pyrithione); tetramethylthiuram disulfide; 2,4,6-trichlorophenylmaleimide; 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine;3-iodo-2-propylbutyl carbamate; diiodomethyl-para-trisulfone;phenyl(bispyridyl)bismuth dichloride; 2-(4-thiazolyl)-benzimidazole;triphenylboronpyridine salt; stearylamine-triphenylboron;laurylamine-triphenylboron; his dimethyl dithiocarbamoyl zincethylenebisdithiocarbamate;1,1-dichloro-N-[(dimethylamino)sulfonyl]-1-fluoro-N-phenylmethanesulfenamide;1,1-dichloro-N-[(dimethylamino)sulfonyl]-1-fluoro-N-(4-methylphenyl)methanesulfeneamide:N′-(3,4-dichlorophenyl)-N,N′-dimethyl urea;N′-tert-butyl-N-cyclopropyl-6-(methylthio)-1,3,5-triazine-2,4-diamine;and4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrileand so on can be recited. These antifouling agents may be used alone orin combination of two or more kinds.

The content of the antifouling agent may be 20 parts by mass or less per100 parts by mass of the total amount of the hydrolyzable resin (i) andthe thermoplastic resin and/or plasticizer (ii) (that is, thehydrolyzable resin (i), the thermoplastic resin and the plasticizer).When the content of the antifouling agent is more than 20 parts by mass,defects such as cracking and peeling can arise in the coating film.

[Other Additives]

The antifouling coating composition of the present invention may containother additives than the hydrolyzable resin (i) and the thermoplasticresin and/or plasticizer (ii). As other additives, for example, apigment, a solvent, a water binder, an anti-sagging agent, ananti-flooding agent, an anti-settling agent, a defoaming agent, acoating film exhaustion conditioner, a UV absorber, a surfaceconditioner, a viscosity conditioner, a leveling agent, a pigmentdisperser and so on can be recited.

As the pigment, for example, extender pigments such as sedimentarybarium, talc, clay, chalk, silica white, alumina white, bentonite,calcium carbonate, magnesium carbonate, silicic acid, silicates,aluminum oxide hydrates and calcium sulfate; and coloring pigments suchas titanium oxide, zircon oxide, basic lead sulfate, tin oxide, carbonblack, white lead, graphite, zinc sulfide, zinc oxide, chromic oxide,yellow nickel titanium, yellow chromium titanium, yellow iron oxide, rediron oxide, black iron oxide, azoic red and yellow pigment, chromiumyellow, phthalocyanine green, phthalocyanine blue, ultramarine blue andquinacridone can be recited. These pigments may be used alone or incombination of two or more kinds.

As the solvent, for example, hydrocarbons such as toluene, xylene,ethylbenzene, cyclopentane, octane, heptane, cyclohexane and whitespirit; ethers such as dioxane, tetrahydrofuran, ethylene glycolmonomethyl ether, ethylene glycol monoethyl ether, ethylene glycolmonobutyl ether, ethylene glycol dibutyl ether, diethylene glycolmonomethyl ether and diethylene glycol monoethyl ether; esters such asbutyl acetate, propyl acetate, benzyl acetate, ethylene glycolmonomethyl ether acetate and ethylene glycol monoethyl ether acetate;ketones such as ethylisobutyl ketone and methylisobutyl ketone; alcoholssuch as n-butanol and propyl alcohol; and the like can be recited. Thesesolvents may be used alone or in combination of two or more kinds.

The antifouling coating composition of the present invention may beprepared, for example, by adding, to the hydrolyzable resin (i) or aresin composition containing the same, the thermoplastic resin and/orplasticizer (ii), and optionally an antifouling agent, and otheradditives such as a pigment and a solvent as necessary, and mixing themby using a mixing machine such as a ball mill, a pebble mill, a rollmill, a sand grinding mill, or a high-speed disperser.

As described above, according to the antifouling coating composition ofthe present invention, since the hydrolyzable resin (i) itself servingas a vehicle exhibits excellent antifouling performance, it is possibleto eliminate the antifouling agent that is separately blended, or toreduce the blending amount thereof. As a result, it is possible toachieve reduction in specific gravity of the antifouling coatingcomposition (paint specific gravity). The reduced paint specific gravityallows reduction in weight of the antifouling coating compositionrequired for forming a coating film of a certain volume, and this allowsreduction in the number of paint cans required for applying a certainvolume when the paint is sold by weight, and is advantageous ineffective utilization of resources and improvement in transportationefficiency.

More concretely, while conventional mainstreams were antifouling coatingcompositions mainly containing a large amount of cuprous oxide as anantifouling agent, the paint specific gravity was as high as about 1.5to 1.8 because the specific gravity of cuprous oxide was as high asabout 5.9. According to the present invention, by not blending anantifouling agent having high specific gravity such as cuprous oxide, orreducing the blending amount thereof, it is possible to reduce the paintspecific gravity to about 1.0 to 1.1. Assuming the dry film thickness ofthe coating film be 100 urn, the theoretical application amount (kg) ofa paint per 1 m² of application area is represented by the followingformula:

Theoretical application amount (kg)=10×paint specificgravity/nonvolatile content volume ratio (%)

Here, the nonvolatile content volume ratio (%) means a solid content interms of volume of the paint. According to the above formula, assumingthe nonvolatile content volume ratio be 50%. the theoretical applicationamount of the paint having a paint specific gravity of 1.0 is 0.2 kg,and the theoretical application amount of the paint having a paintspecific gravity of 1.6 is 0.32 kg. In this manner, according to thepresent invention, it is possible to reduce the use weight of the paintrequired for coating an object to be coated.

<Antifouling Film and Composite Film>

The antifouling film of the present invention can be formed by applyingthe antifouling coating composition on a surface of an object to becoated according to a routine method, and then removing a solvent byvolatilization at room temperature or under heating as necessary. Theapplication method is not particularly limited, and for example,conventionally known methods such as a dipping method, a spray method,brush application, a roller, electrostatic coating, andelectrodeposition coating can be recited. Examples of the object to becoated include, but are not limited to, ships; fish nets typically forfarming and other fishing equipment; harbor facilities; offences; intakeequipment of an electric generation plant or the like; piping such aswater conduits for cooling; bridges, buoyage; industrial water systemfacilities; and submarine bases. The antifouling film formed by usingthe antifouling coating composition of the present invention has anexcellent long-term antifouling property and excellent crack resistance.Also adherence with a base is excellent. An application surface of theobject to be coated may be pretreated as necessary, or on a primer filmof another paint such as an antirust paint (anticorrosion paint) formedon an object to be coated, an antifouling film formed from theantifouling coating composition of the present invention may he formedto produce a composite film.

Here, as described above. according to the antifouling coatingcomposition of the present invention, since the hydrolyzable resin (i)itself serving as a vehicle exhibits excellent antifouling performance.the antifouling agent that is separately blended can be eliminated. orthe blending amount thereof can he reduced. Therefore, by theantifouling coating composition of the present invention, it is possibleto form a clear (highly transparent) antifouling film. An antifoulingfilm formed from a conventional antifouling coating composition mainlycontaining a large amount of cuprous oxide as an antifouling agentgenerally takes on a reddish color phase due to the contained cuprousoxide, and the color phase thereof is limited, however, according to thepresent invention, various applications utilizing the transparency ofthe obtained antifouling film are possible. In forming a clearantifouling film, it is preferred that the antifouling coatingcomposition of the present invention does not contain a coloringpigment.

For example, in the composite film having a primer film formed from anantirust paint or the like and an antifouling film of the presentinvention formed on the primer film, by using a clear antifouling filmas the antifouling film and those having various color phases as theantirust paint, it is possible to provide a coated object such as anin-water structure having a composite film-formed surface having a colorphase that is not conventionally realized, while having an antifoulingproperty. Also by forming an intermediate film of a paint having variouscolor phases between the primer film of an antirust paint or the likeand the clear antifouling film, it is possible to provide a coatedobject having a color phase that is not conventionally realized. As thepaint forming the intermediate film, for example, various paints such asan antifouling paint, an epoxy resin paint, a urethane resin paint, anacrylic resin paint, a chlorinated rubber paint, an alkyd resin paint, asilicon resin paint, and a fluorine resin paint may be used. Theantifouling paint forming the intermediate film may be the antifoulingcoating composition of the present invention, or a different antifoulingcoating composition such as a conventional antifouling coatingcomposition containing a relatively large amount of antifouling agent.The intermediate film may be formed on the entire surface of the primerfilm, or may be formed on part of the surface. The intermediate film andthe primer film may be a used old coating film. In this case, theantifouling film of the present invention may be used for repairing theold coating film.

Also by forming the intermediate film between the primer film of anantirust paint or the like and the clear antifouling film into the formof, for example, a character, pattern, design, or picture having variouscolor phases, various design features can be imparted to the coatedobject. Also by interposing a film or a seal member in the form of acharacter, pattern, design, or picture having various color phases, inplace of the intermediate film interposed between the primer film andthe clear antifouling film, various design features can be imparted tothe coated object.

EXAMPLES

In the following, the present invention will be described morespecifically by way of examples and comparative examples, however, it isto be noted that the present invention will not be limited to these.

[1] Preparation of Metal-Atom-Containing Polymerizable Monomer (b)Production Example M1 Preparation of Metal-Atom-Containing PolymerizableMonomer Mixture M1

A four-neck flask equipped with a condenser, a thermometer, a droppingfunnel and a stirrer was charged with 85.4 parts by mass of PGM(propylene glycol methyl ether) and 40.7 parts by mass of zinc oxide,and the temperature was raised to 75° C. under stirring. Then, from thedropping funnel, a mixture of 43.1 parts by mass of methacrylic acid,36.1 parts by mass of acrylic acid and 5 parts by mass of water wasdropped at a constant velocity over 3 hours. After further stirring for2 hours, 36 parts by mass of PGM was added, to obtain a transparentmetal-atom-containing polymerizable monomer mixture M1. The solidcontent was 44.8% by mass. The metal-atom-containing polymerizablemonomer mixture M1 contains zinc (meth)acrylate which is the monomer(b2) as the metal-atom-containing polymerizable monomer (b).

Production Example M2 Preparation of Metal-Atom-Containing PolymerizableMonomer Mixture M2

A four-neck flask equipped with a condenser, a thermometer, a droppingfunnel and a stirrer was charged with 72.4 parts by mass of PGM and 40.7parts by mass of zinc oxide. and the temperature was raised to 75° C.under stirring. Then, from the dropping funnel, a mixture of 30.1 partsby mass of methacrylic acid, 25.2 parts by mass of acrylic acid and 51.6parts by mass of versatic acid was dropped at a constant velocity over 3hours. After further stirring for 2 hours, 11 parts by mass of PGM wasadded, to obtain a transparent metal-atom-containing polymerizablemonomer mixture M2. The solid content was 59.6% by mass. Themetal-atom-containing polymerizable monomer mixture M2 contains, as themetal-atom-containing polymerizable monomer (b), zinc (meth)acrylatewhich is the monomer (b1) represented by the general formula (V′) (R³⁰is a versatic acid residue), and zinc (meth)acrylate which is themonomer (b2).

Production Example M3 Preparation of Metal-Atom-Containing PolymerizableMonomer Mixture M3

A four-neck flask equipped with a condenser, a thermometer, a droppingfunnel and a stirrer was charged with 60 parts by mass of xylene, 13parts by mass of PGM and 40.7 parts by mass of zinc oxide, and thetemperature was raised to 75° C. under stirring. Then, from the droppingfunnel, a mixture of 32.3 parts by mass of methacrylic acid, 27 parts bymass of acrylic acid, 37.7 parts by mass of oleic acid. 2.3 parts bymass of acetic acid and 5.8 parts by mass of propionic acid was droppedat a constant velocity over 3 hours. After further stirring for 2 hours.77 parts by mass of xylene and 46 parts by mass of PGM were added, toobtain a transparent metal-atom-containing polymerizable monomer mixtureM3. The solid content was 39.6% by mass. The metal-atom-containingpolymerizable monomer mixture M3 contains, as the metal-atom-containingpolymerizable monomer (b), zinc (meth)acrylate which is the monomer (b1)represented by the general formula (V′) (R³⁰ is at least one kind of anoleic acid residue, an acetic acid residue, and a propionic acidresidue) and zinc (meth)acrylate which is the monomer (b2).

[2] Preparation of Hydrolyzable Resin Production Example S1 Preparationof Hydrolyzable Resin Composition S1

A four-neck flask equipped with a condenser, a thermometer, a droppingfunnel and a stirrer was charged with 15 parts by mass of POM, 65 partsby mass of xylene and 4 parts by mass of ethyl acrylate, and thetemperature was raised to 100° C. under stirring. Then. from thedropping funnel, a mixture of 32.3 parts by mass of methyl methacrylate,43.9 parts by mass of ethyl acrylate, 10 parts by mass of “FM-0721”(product of CHISSO CORPORATION), 21.7 parts by mass of themetal-atom-containing polymerizable monomer mixture M1 of ProductionExample M1, 10 parts by mass of xylene, 1.2 parts by mass of a chaintransfer agent (α-methylstyrene dimer), 2.5 parts by mass ofazobisisobutyronitrile (AIBN) and 3 parts by mass ofazobismethylbutyronitrile (AMBN) was dropped at a constant velocity over6 hours. After end of the dropping, 0.5 parts by mass oft-butylperoctoate and 10 parts by mass of xylene were dropped over 30minutes, and after further stirring for 1 hour and 30 minutes, 10.1parts by mass of xylene was added to obtain a hydrolyzable resincomposition S1.

The obtained hydrolyzable resin composition S1 was analyzed by GPC(“HLC-8220GPC” available from TOSOH CORPORATION, eluent:dimethylformamide) and the weight average molecular weight of thehydrolyzable resin contained in the hydrolyzable resin composition S1was 6800 in terms of polystyrene. The hydrolyzable resin isolated fromthe obtained hydrolyzable resin composition S1 by methanolreprecipitation was collected into a platinum crucible, added withsulfuric acid, and then heated in a pressurized decomposition vessel.After volatilizing sulfuric acid, the hydrolyzable resin was completelyashed. The ashed matter was subjected to alkaline fusion after leftstanding to cool, and analyzed by an ICP emission analyzer (“SPS5100”available from Seiko Instruments inc.) to find a Si atom. Also, thehydrolyzable resin was analyzed by an atomic absorptionspectrophotometer (“AA6300” available from Shimadzu Corporation) to finda signal from a Zn atom.

Production Example S2 Preparation of Hydrolyzable Resin Composition S2

A four-neck flask equipped with a condenser, a thermometer, a droppingfunnel and a stirrer was charged with 15 parts by mass of PGM, 65 partsby mass of xylene and 4 parts by mass of ethyl acrylate, and thetemperature was raised to 100° C. under stirring. Then, from thedropping funnel, a mixture of 32.3 parts by mass of methyl methacrylate,13.9 parts by mass of ethyl acrylate, 40 parts by mass of “FM-0711”(product of CHISSO CORPORATION), 21.7 parts by mass of themetal-atom-containing polymerizable monomer mixture M1 of ProductionExample M1. 10 parts by mass of xylene, 1.2 parts by mass of a chaintransfer agent (α-methylstyrene dimer), 2.5 parts by mass of AIBN and0.8 parts by mass of AMBN was dropped at a constant velocity over 6hours. After end of the dropping, 0.5 parts by mass of t-butylperoctoateand 10 parts by mass of xylene were dropped over 30 minutes, and themixture was further stirred for 1 hour and 30 minutes, and then addedwith 10.1 parts by mass of xylene, to obtain a hydrolyzable resincomposition S2.

The obtained hydrolyzable resin composition S2 was analyzed by GPC(“HLC-8220GPC” available from TOSOH CORPORATION, eluent:dimethylformamide), and the weight average molecular weight of thehydrolyzable resin contained in the hydrolyzable resin composition S2was 8800 in terms of polystyrene.

Production Example S3 Preparation of Hydrolyzable Resin Composition S3

A four-neck flask equipped with a condenser, a thermometer, a droppingfunnel and a stirrer was charged with 15 parts by mass of PGM and 61parts by mass of xylene, and the temperature was raised to 100° C. understirring. Then, from the dropping funnel, a mixture of 18 parts by massof methyl methacrylate, 25 parts by mass of ethyl acrylate, 40 parts bymass of “X-24-8201” (product of Shin-Etsu Chemical Co., Ltd.), 28.4parts by mass of the metal-atom-containing polymerizable monomer mixtureM2 of Production Example M2, 20 parts by mass of PGM, 2.5 parts by massof AIBN and 1 part by mass of AMBN was dropped at a constant velocityover 4 hours. After end of the dropping, 0.5 parts by mass oft-butylperoctoate and 10 parts by mass of xylene were dropped over 30minutes, and the mixture was further stirred for 1 hour and 30 minutes,and then added with 4.6 parts by mass of xylene, to obtain ahydrolyzable resin composition S3.

The obtained hydrolyzable resin composition S3 was analyzed by GPC(“HLC-8220GPC” available from TOSOH CORPORATION, eluent:dimethylformamide), and the weight average molecular weight of thehydrolyzable resin contained in the hydrolyzable resin composition S3was 8200 in terms of polystyrene.

Production Example S4 Preparation of Hydrolyzable Resin Composition S4

A four-neck flask equipped with a condenser, a thermometer, a droppingfunnel and a stirrer was charged with 35 parts by mass of PGM and 41parts by mass of xylene, and the temperature was raised to 100° C. understirring. Then, from the dropping funnel, a mixture of 18 parts by massof methyl methacrylate, 15 parts by mass of ethyl acrylate, 50 parts bymass of “X-24-8201” (product of Shin-Etsu Chemical Co Ltd.), 42.5 partsby mass of the metal-atom-containing polymerizable monomer mixture M3 ofProduction Example M3, 5 parts by mass of PGM, 2.5 parts by mass of AIBNand 1 part by mass of AMBN was dropped at a constant velocity over 6hours. After end of the dropping, 0.5 parts by mass of t-butylperoctoateand 10 parts by mass of xylene were dropped over 30 minutes, and themixture was further stirred for 1 hour and 30 minutes, and then addedwith 5.5 parts by mass of xylene, to obtain a hydrolyzable resincomposition S4.

The obtained hydrolyzable resin composition S4 was analyzed by GPC(“HLC-8220GPC” available from TOSOH CORPORATION, eluent:dimethylformamide), and the weight average molecular weight of thehydrolyzable resin contained in the hydrolyzable resin composition S4was 7200 in terms of polystyrene.

Production Example S5 Preparation of Hydrolyzable Resin Composition S5

A four-neck flask equipped with a condenser, a thermometer, a droppingfunnel and a stirrer was charged with 15 parts by mass of PGM, 59 partsby mass of xylene and 4 parts by mass of ethyl acrylate, and thetemperature was raised to 100° C. under stirring. Then, from thedropping funnel, a mixture of 26.4 parts by mass of methyl methacrylate,25.5 parts by mass of ethyl acrylate, 30 parts by mass of asilicon-containing monomer A. 31.3 parts by mass of themetal-atom-containing polymerizable monomer mixture M1 of ProductionExample M1, 10 parts by mass of xylene, 1.5 parts by mass of a chaintransfer agent (α-methylstyrene dimer), 2.5 parts by mass of AIBN and 4parts by mass of AMBN was dropped at a constant velocity over 6 hours.After end of the dropping. 0.5 parts by mass of t-butylperoctoate and 10parts by mass of xylene were dropped over 30 minutes, and the mixturewas further stirred for 1 hour and 30 minutes. and then added with 10.8parts by mass of xylene. to obtain a hydrolyzable resin composition S5.

The obtained hydrolyzable resin composition S5 was analyzed by GPC(“HLC-8220GPC” available from TOSOH CORPORATION, eluent:dimethylformamide), and the weight average molecular weight of thehydrolyzable resin contained in the hydrolyzable resin composition S5was 6400 in terms of polystyrene.

Production Example S6 Preparation of Hydrolyzable Resin Composition S6

A four-neck flask equipped with a condenser, a thermometer, a droppingfunnel and a stirrer was charged with 15 parts by mass of PGM, 59 partsby mass of xylene and 4 parts by mass of ethyl acrylate, and thetemperature was raised to 100° C. under stirring. Then, from thedropping funnel, a mixture of 21.4 parts by mass of methyl methacrylate.25.5 parts by mass of ethyl acrylate, 5 parts by mass of styrene. 30parts by mass of a silicon-containing monomer B, 31.3 parts by mass ofthe metal-atom-containing polymerizable monomer mixture M1 of ProductionExample M1, 10 parts by mass of xylene, 1.5 parts by mass of a chaintransfer agent (α-methylstyrene dimer), 2.5 parts by mass of AIBN and2.5 parts by mass of AMBN was dropped at a constant velocity over 6hours. After end of the dropping, 0.5 parts by mass of t-butylperoctoateand 10 parts by mass of xylene were dropped over 30 minutes, and themixture was further stirred for 1 hour and 30 minutes, and then addedwith 10.8 parts by mass of xylene, to obtain a hydrolyzable resincomposition S6.

The obtained hydrolyzable resin composition S6 was analyzed by GPC(“HLC-8220GPC” available from TOSOH CORPORATION, eluent:dimethylformamide), and the weight average molecular weight of thehydrolyzable resin contained in the hydrolyzable resin composition S6was 6900 in terms of polystyrene.

Production Example S7 Preparation of Hydrolyzable Resin Composition S7

A four-neck flask equipped with a condenser, a thermometer, a droppingfunnel and a stirrer was charged with 15 parts by mass of PGM, 59 partsby mass of xylene and 4 parts by mass of ethyl acrylate, and thetemperature was raised to 100° C. under stirring. Then, from thedropping funnel, a mixture of 26.4 parts by mass of methyl methacrylate.14.5 parts by mass of ethyl acrylate, 5 parts by mass of 2-methoxyethylacrylate, 20 parts by mass of “FM-0711” (product of CHISSO CORPORATION),20 parts by mass of “TM-0701” (product of CHISSO CORPORATION), 31.3parts by mass of the metal-atom-containing polymerizable monomer mixtureM1 of Production Example M1, 10 parts by mass of xylene, 1.5 parts bymass of a chain transfer agent (α-methylstyrene dimer), 2.5 parts bymass of AIBN and 2.5 parts by mass of AMBN was dropped at a constantvelocity over 6 hours. After end of the dropping, 0.5 parts by mass oft-butylperoctoate and 10 parts by mass of xylene were dropped over 30minutes, and the mixture was further stirred for 1 hour and 30 minutes,and then added with 10.8 parts by mass of xylene, to obtain ahydrolyzable resin composition S7.

The obtained hydrolyzable resin composition S7 was analyzed by GPC(“HLC-8220GPC” available from TOSOH CORPORATION, eluent:dimethylformamide), and the weight average molecular weight of thehydrolyzable resin contained in the hydrolyzable resin composition S7was 7000 in terms of polystyrene.

Production Example S8 Preparation of Hydrolyzable Resin Composition S8

A four-neck flask equipped with a condenser, a thermometer, a droppingfunnel and a stirrer was charged with 15 parts by mass of PGM and 61parts by mass of xylene. and the temperature was raised to 100° C. understirring. Then, from the dropping funnel, a mixture of 18 parts by massof methyl methacrylate, 35 parts by mass of ethyl acrylate, 30 parts bymass of a silicon-containing, monomer C, 28.4 parts by mass of themetal-atom-containing polymerizable monomer mixture M2 of ProductionExample M2, 20 parts by mass of PGM, 2.5 parts by mass of AIBN and 2parts by mass of AMBN was dropped at a constant velocity over 4 hours.After end of the dropping, 0.5 parts by mass of t-butylperoctoate and 10parts by mass of xylene were dropped over 30 minutes. and the mixturewas further stirred for 1 hour and 30 minutes, and then added with 4.6parts by mass of xylene, to obtain a hydrolyzable resin composition S8.

The obtained hydrolyzable resin composition S8 was analyzed by GPC(“HLC-8220GPC” available from TOSOH CORPORATION, eluent:dimethylformamide), and the weight average molecular weight of thehydrolyzable resin contained in the hydrolyzable resin composition S8was 7700 in terms of polystyrene.

Production Example S9 Preparation of Hydrolyzable Resin Composition S9

A four-neck flask equipped with a condenser, a thermometer, a droppingfunnel and a stirrer was charged with 15 parts by mass of PGM, 59 partsby mass of xylene and 4 parts by mass of ethyl acrylate, and thetemperature was raised to 100° C. under stirring. Then, from thedropping funnel, a mixture of 26.4 parts by mass of methyl methacrylate,35.5 parts by mass of ethyl acrylate, 20 parts by mass of asilicon-containing monomer D. 31.3 parts by mass of themetal-atom-containing polymerizable monomer mixture M1 of ProductionExample M1, 10 parts by mass of xylene, 1.5 parts by mass of a chaintransfer agent (α-methylstyrene dimer), 2.5 parts by mass of AIBN and5.5 parts by mass of AMBN was dropped at a constant velocity over 6hours. After end of the dropping, 0.5 parts by mass of t-butylperoctoateand 10 parts by mass of xylene were dropped over 30 minutes, and themixture was further stirred for 1 hour and 30 minutes. and then addedwith 10.8 parts by mass of xylene, to obtain a hydrolyzable resincomposition S9.

The obtained hydrolyzable resin composition S9 was analyzed by GPC(“HLC-8220GPC” available from TOSOH CORPORATION, eluent:dimethylformamide), and the weight average molecular weight of thehydrolyzable resin contained in the hydrolyzable resin composition S9was 6000 in terms of polystyrene.

Production Example S10 Preparation of Hydrolyzable Resin Composition S10

A four-neck flask equipped with a condenser, a thermometer, a droppingfunnel and a stirrer was charged with 15 parts by mass of PGM, 65 partsby mass of xylene and 4 parts by mass of ethyl acrylate. and thetemperature was raised to 100° C. under stirring. Then, from thedropping funnel, a mixture of 32.3 parts by mass of methyl methacrylate,43.9 parts by mass of ethyl acrylate, 10 parts by mass of “FM-7711”(product of CHISSO CORPORATION), 21.7 parts by mass of themetal-atom-containing polymerizable monomer mixture M1 of ProductionExample M1, 10 parts by mass of xylene, 2 parts by mass of a chaintransfer agent (α-methylstyrene dimer), 2.5 parts by mass of AIBN and7.5 parts by mass of AMBN was dropped at a constant velocity over 6hours. After end of the dropping, 0.5 parts by mass of t-butylperoctoateand 10 parts by mass of xylene were dropped over 30 minutes, and themixture was further stirred for 1 hour and 30 minutes, and then addedwith 10.1 parts by mass of xylene, to obtain a hydrolyzable resincomposition S10.

The obtained hydrolyzable resin composition S10 was analyzed by GPC(“HLC-8220GPC” available from TOSOH CORPORATION, eluent:dimethylformamide), and the weight average molecular weight of thehydrolyzable resin contained in the hydrolyzable resin composition S10was 5400 in terms of polystyrene. The hydrolyzable resin isolated fromthe obtained hydrolyzable resin composition S10 by methanolreprecipitation was collected into a platinum crucible, added withsulfuric acid, and then heated in a pressurized decomposition vessel.After volatilizing sulfuric acid. the hydrolyzable resin was completelyashed. The ashed matter was subjected to alkaline fusion after leftstanding to cool, and analyzed by an ICP emission analyzer (“SPS5100”available from Seiko Instruments inc.) to find a Si atom. Also, thehydrolyzable resin was analyzed by an atomic absorptionspectrophotometer (“AA6300” available from Shimadzu Corporation) to finda signal from a Zn atom.

Production Example S11 Preparation of Hydrolyzable Resin Composition S11

A four-neck flask equipped with a condenser, a thermometer, a droppingfunnel and a stirrer was charged with 15 parts by mass of PGM, 65 partsby mass of xylene and 4 parts by mass of ethyl acrylate, and thetemperature was raised to 100° C. under stirring. Then, from thedropping funnel, a mixture of 32.3 parts by mass of methyl methacrylate.33.9 parts by mass of ethyl acrylate, 20 parts by mass of “FM-7721”(product of CHISSO CORPORATION), 21.7 parts by mass of themetal-atom-containing polymerizable monomer mixture M1 of ProductionExample M1, 10 parts by mass of xylene, 1.5 parts by mass of a chaintransfer agent (α-methylstyrene dimer). 2.5 parts by mass of AIBN and 5parts by mass of AMBN was dropped at a constant velocity over 6 hours.After end of the dropping, 0.5 parts by mass of t-butyl peroctoate and10 parts by mass of xylene were dropped over 30 minutes, and the mixturewas further stirred for 1 hour and 30 minutes, and then added with 10.1parts by mass of xylene, to obtain a hydrolyzable resin composition S11.

The obtained hydrolyzable resin composition S11 was analyzed by GPC(“HLC-8220GPC” available from TOSOH CORPORATION, eluent:dimethylformamide), and the weight average molecular weight of thehydrolyzable resin contained in the hydrolyzable resin composition S11was 6200 in terms of polystyrene.

Production Example S12 Preparation of Hydrolyzable Resin Composition S12

A four-neck flask equipped with a condenser, a thermometer, a droppingfunnel and a stirrer was charged with 15 parts by mass of PGM, 59 partsby mass of xylene and 4 parts by mass of ethyl acrylate, and thetemperature was raised to 100° C. under stirring. Then, from thedropping funnel, a mixture of 26.4 parts by mass of methyl methacrylate,40.5 parts by mass of ethyl acrylate, 15 parts by mass of asilicon-containing monomer E, 31.3 parts by mass of themetal-atom-containing polymerizable monomer mixture M1 of ProductionExample M1, 10 parts by mass of xylene, 2 parts by mass of a chaintransfer agent (α-methylstyrene dimer), 2.5 parts by mass of AIBN and 8parts by mass of AMBN was dropped at a constant velocity over 6 hours.After end of the dropping, 0.5 parts by mass of t-butylperoctoate and 10parts by mass of xylene were dropped over 30 minutes, and the mixturewas further stirred for 1 hour and 30 minutes, and then added with 10.8parts by mass of xylene, to obtain a hydrolyzable resin composition S12.

The obtained hydrolyzable resin composition S12 was analyzed by GPC(“HLC-8220GPC” available from TOSOH CORPORATION, eluent:dimethylformamide), and the weight average molecular weight of thehydrolyzable resin contained in the hydrolyzable resin composition S12was 5600 in terms of polystyrene.

Production Example S13 Preparation of Hydrolyzable Resin Composition S13

A four-neck flask equipped with a condenser, a thermometer, a droppingfunnel and a stirrer was charged with 15 parts by mass of PGM, 59 partsby mass of xylene and 4 parts by mass of ethyl acrylate, and thetemperature was raised to 100° C. under stirring. Then, from thedropping funnel, a mixture of 26.4 parts by mass of methyl methacrylate,35,5 parts by mass of ethyl acrylate, 20 parts by mass of asilicon-containing monomer F, 31.3 parts by mass of themetal-atom-containing polymerizable monomer mixture M1 of ProductionExample M1, 10 parts by mass of xylene, 1.5 parts by mass of a chaintransfer agent (α-methylstyrene dimer), 2.5 parts by mass of AIBN and7.5 parts by mass of AMBN was dropped at a constant velocity over 6hours. After end of the dropping, 0.5 parts by mass of t-butylperoctoateand 10 parts by mass of xylene were dropped over 30 minutes. and themixture was further stirred for 1 hour and 30 minutes, and then addedwith 10.8 parts by mass of xylene, to obtain a hydrolyzable resincomposition S13.

The obtained hydrolyzable resin composition S 13 was analyzed by GPC(“HLC-8220GPC” available from TOSOH CORPORATION, eluent:dimethylformamide), and the weight average molecular weight of thehydrolyzable resin contained in the hydrolyzable resin composition S13was 5500 in terms of polystyrene.

Production Example S14 Preparation of Hydrolyzable Resin Composition S14

A four-neck flask equipped with a condenser, a thermometer, a droppingfunnel and a stirrer was charged with 15 parts by mass of PGM, 65 partsby mass of xylene and 4 parts by mass of ethyl acrylate, and thetemperature was raised to 100° C. under stirring. Then, from thedropping funnel, a mixture of 32.3 parts by mass of methyl methacrylate.13.9 parts by mass of ethyl acrylate, 5 parts by mass of “FM 7711”(product of CHISSO CORPORATION), 35 parts by mass of “FM-0711” (productof CHISSO CORPORATION), 21.7 parts by mass of the metal-atom-containingpolymerizable monomer mixture M1 of Production Example M1, 10 parts bymass of xylene, 1.2 parts by mass of a chain transfer agent(α-methylstyrene dimer), 2.5 parts by mass of AIBN and 4 parts by massof AMBN was dropped at a constant velocity over 6 hours. After end ofthe dropping, 0.5 parts by mass of t-butylperoctoate and 10 parts bymass of xylene were dropped over 30 minutes, and the mixture was furtherstirred for 1 hour and 30 minutes, and then added with 10.1 parts bymass of xylene. to obtain a hydrolyzable resin composition S14.

The obtained hydrolyzable resin composition S14 was analyzed by GPC(“HLC-8220GPC” available from TOSOH CORPORATION, eluent:dimethylformamide), and the weight average molecular weight of thehydrolyzable resin contained in the hydrolyzable resin composition S14was 9000 in terms of polystyrene.

Production Example S15 Preparation of Hydrolyzable Resin Composition S15

A four-neck flask equipped with a condenser, a thermometer, a droppingfunnel and a stirrer was charged with 35 parts by mass of PGM and 31parts by mass of xylene, and the temperature was raised to 100° C. understirring. Then, from the dropping funnel, a mixture of 18 parts by massof methyl methacrylate, 25 parts by mass of ethyl acrylate, 10 parts bymass of “FM-7721” (product of CHISSO CORPORATION), 30 parts by mass of“X-24-8201” (product of Shin-Etsu Chemical Co., Ltd.), 28.4 parts bymass of the metal-atom-containing polymerizable monomer mixture M2 ofProduction Example M2, 30 parts by mass of xylene, 2.5 parts by mass ofAIBN and 2.5 parts by mass of AMBN was dropped at a constant velocityover 4 hours. After end of the dropping, 0.5 parts by mass oft-butylperoctoate and 10 parts by mass of xylene were dropped over 30minutes, and the mixture was further stirred for 1 hour and 30 minutes,and then added with 4.6 parts by mass of xylene, to obtain ahydrolyzable resin composition S15.

The obtained hydrolyzable resin composition S15 was analyzed by GPC(“HLC-8220GPC” available from TOSOH CORPORATION, eluent:dimethylformamide), and the weight average molecular weight of thehydrolyzable resin contained in the hydrolyzable resin composition S15was 7200 in terms of polystyrene.

Production Example S16 Preparation of Hydrolyzable Resin Composition S16

A four-neck flask equipped with a condenser, a thermometer, a droppingfunnel and a stirrer was charged with 40 parts by mass of PGM and 31parts by mass of xylene, and the temperature was raised to 100° C. understirring. Then, from the dropping funnel, a mixture of 18 parts by massof methyl methacrylate, 15 parts by mass of ethyl acrylate, 10 parts bymass of “FM-7711” (product of CHISSO CORPORATION), 10 parts by mass of“FM-7721” (product of CHISSO CORPORATION), 30 parts by mass of “FM-0711”(product of CHISSO CORPORATION), 42.5 parts by mass of themetal-atom-containing polymerizable monomer mixture M3 of ProductionExample M3, 10 parts by mass of xylene, 2.5 parts by mass of AIBN and4.5 parts by mass of AMBN was dropped at a constant velocity over 6hours. After end of the dropping, 0.5 parts by mass of t-butylperoctoateand 10 parts by mass of xylene were dropped over 30 minutes, and themixture was further stirred for 1 hour and 30 minutes, and then addedwith 5.5 parts by mass of xylene, to obtain a hydrolyzable resincomposition S16.

The obtained hydrolyzable resin composition S16 was analyzed by GPC(“HLC-8220GPC” available from TOSOH CORPORATION, eluent:dimethylformamide), and the weight average molecular weight of thehydrolyzable resin contained in the hydrolyzable resin composition S16was 6400 in terms of polystyrene.

Production Example S17 Preparation of Hydrolyzable Resin Composition S17

A four-neck flask equipped with a condenser, a thermometer, a droppingfunnel and a stirrer was charged with 15 parts by mass of PGM, 59 partsby mass of xylene and 4 parts by mass of ethyl acrylate, and thetemperature was raised to 100° C. under stirring. Then, from thedropping funnel, a mixture of 26.4 parts by mass of methyl methacrylate,15.5 parts by mass of ethyl acrylate, 2 parts by mass of asilicon-containing monomer G. 38 parts by mass of the silicon-containingmonomer ID. 31.3 parts by mass of the metal-atom-containingpolymerizable monomer mixture M1 of Production Example M1, 10 parts bymass of xylene, 1.2 parts by mass of a chain transfer agent(α-methylstyrene dimer), 2.5 parts by mass of AIBN and 5.5 parts by massof AMBN was dropped at a constant velocity over 6 hours. After end ofthe dropping, 0.5 parts by mass of t-hutylperoctoate and 10 parts bymass of xylene were dropped over 30 minutes, and the mixture was furtherstirred for 1 hour and 30 minutes, and then added with 10.8 parts bymass of xylene, to obtain a hydrolyzable resin composition S17.

The obtained hydrolyzable resin composition S17 was analyzed by GPC(“HLC-8220GPC” available from TOSOH CORPORATION, eluent:dimethylformamide), and the weight average molecular weight of thehydrolyzable resin contained in the hydrolyzable resin composition S17was 5600 in terms of polystyrene.

Production Example S18 Preparation of Hydrolyzable Resin Composition S18

A four-neck flask equipped with a condenser, a thermometer, a droppingfunnel and a stirrer was charged with 35 parts by mass of PGM and 31parts by mass of xylene, and the temperature was raised to 100° C. understirring. Then, from the dropping funnel, a mixture of 18 parts by massof methyl methacrylate, 45 parts by mass of ethyl acrylate, 10 parts bymass of the silicon-containing monomer G, 10 parts by mass of “TM-0701”(product of CHISSO CORPORATION), 28.4 parts by mass of themetal-atom-containing polymerizable monomer mixture M2 of ProductionExample M2, 30 parts by mass of xylene, 2.5 parts by mass of AIBN and 5parts by mass of AMBN was dropped at a constant velocity over 4 hours.After end of the dropping. 0.5 parts by mass of t-butylperoctoate and 10parts by mass of xylene were dropped over 30 minutes, and the mixturewas further stirred for 1 hour and 30 minutes. and then added with 4.6parts by mass of xylene, to obtain a hydrolyzable resin composition S18.

The obtained hydrolyzable resin composition S18 was analyzed by GPC(“HLC-8220GPC” available from TOSOH CORPORATION, eluent:dimethylformamide). and the weight average molecular weight of thehydrolyzable resin contained in the hydrolyzable resin composition S18was 6000 in terms of polystyrene.

Production Example T1 Preparation of Resin Composition T1

A four-neck flask equipped with a condenser, a thermometer, a droppingfunnel and a stirrer was charged with 15 parts by mass of PGM and 65parts by mass of xylene. and the temperature was raised to 100° C. understirring. Then, from the dropping funnel, a mixture of 42.1 parts bymass of methyl methacrylate. 37.9 parts by mass of ethyl acrylate, 20parts by mass of “FM-0711” (product of CHISSO CORPORATION), 10 parts bymass of xylene, 11.9 parts by mass of PGM. 1.2 parts by mass of a chaintransfer agent (α-methylstyrene dimer), 2.5 parts by mass of AIBN and 2parts by mass of AMBN was dropped at a constant velocity over 6 hours.After end of the dropping, 0.5 parts by mass of t-butylperoctoate and 10parts by mass of xylene were dropped over 30 minutes, and the mixturewas further stirred for 1 hour and 30 minutes. and then added with 10.1parts by mass of xylene, to obtain a resin composition T1.

The obtained resin composition T1 was analyzed by GPC (“HLC-8220GPC”available from TOSOH CORPORATION, eluent: dimethylformamide), and theweight average molecular weight of the resin contained in the resincomposition T1 was 6200 in terms of polystyrene.

Production Example T2 Preparation of Resin Composition T2

A four-neck flask equipped with a condenser, a thermometer, a droppingfunnel and a stirrer was charged with 15 parts by mass of PGM and 70parts by mass of xylene, and the temperature was raised to 100° C. understirring. Then, from the dropping funnel, a mixture of 42.1 parts bymass of methyl methacrylate, 17.9 parts by mass of ethyl acrylate, 10parts by mass of “FM-7711” (product of CHISSO CORPORATION), 30 parts bymass of “FM-0711” (product of CHISSO CORPORATION), 10 parts by mass ofxylene, 11.9 parts by mass of PGM, 3 parts by mass of a chain transferagent (α-methylstyrene dimer), 2.5 parts by mass of AIBN and 7 parts bymass of AMBN was dropped at a constant velocity over 6 hours. After endof the dropping, 0.5 parts by mass of t-butylperoctoate and 10 parts bymass of xylene were dropped over 30 minutes, and the mixture was furtherstirred for 1 hour and 30 minutes. and then added with 5.1 parts by massof xylene. to obtain a resin composition T2.

The obtained resin composition T2 was analyzed by GPC (“HLC-8220GPC”available from TOSOH CORPORATION, eluent: dimethylformamide), and theweight average molecular weight of the resin contained in the resincomposition T2 was 8600 in terms of polystyrene.

Production Example T3 Preparation of Hydrolyzable Resin Composition T3

A four-neck flask equipped with a stirrer, a condenser, a temperaturecontrol device, a nitrogen introducing tube, and a dropping funnel wascharged with 64 parts by mass of xylene and 16 parts by mass ofn-butanol, and kept at 100° C. The solution was added dropwise with amixed liquid of a monomer according to the formulation (part by mass) ofTable 2 and 2.3 parts by mass of t-butylperoxy-2-ethylhexanoate at aconstant velocity over 3 hours, and retained at this temperature for 30minutes after end of the dropping. Then, a mixed liquid of 16 parts bymass of xylene, 4 parts by mass of n-butanol and 0.2 parts by mass oft-butylperoxy-2-ethylhexanoate was added dropwise at a constant velocityover 30 minutes, and retained at this temperature for 1 hour and 30minutes after end of the dropping, to obtain a resin varnish. The solidcontent in the obtained resin varnish was 49.8% by mass, and the acidvalue of the resin in the resin varnish was 130.

Next, in a similar reaction vessel, 100 parts by mass of the resinvarnish, 25.4 parts by mass of zinc acetate, 39.2 parts by mass ofnaphthenic acid (NA-165, acid value 165 mg KOH/g, product of YamatoYushi Kogyo), and 110 parts by mass of xylene were added, and heated to130° C., and acetic acid was removed together with the solvent, toobtain a hydrolyzable resin composition T3 having a solid content of41.5% by mass.

The obtained hydrolyzable resin composition T3 was analyzed by GPC(“HLC-8220GPC” available from TOSOH CORPORATION, eluent:dimethylformamide), and the weight average molecular weight of thehydrolyzable resin contained in the hydrolyzable resin composition T3was 8000 in terms of polystyrene.

Production Example T4 Preparation of Hydrolyzable Resin Composition T4

A four-neck flask equipped with a stirrer, a condenser, a temperaturecontrol device. a nitrogen introducing tube, and a dropping funnel wascharged with 64 parts by mass of xylene and 16 parts by mass ofn-butanol, and kept at 115° C. The solution was added dropwise with amixed liquid of a monomer according to the formulation (part by mass) ofTable 2 and 3 parts by mass of t-butylperoxy-2-ethylhexanoate at aconstant velocity over 3 hours, and retained at this temperature for 30minutes after end of the dropping. Then, a mixed liquid of 16 parts bymass of xylene, 4 parts by mass of n-butanol and 0.2 parts by mass oft-butylperoxy-2-ethylhexanoate was added dropwise at a constant velocityover 30 minutes, and retained at this temperature for 1 hour and 30minutes after end of the dropping, to obtain a resin varnish. The solidcontent in the obtained resin varnish was 49.7% by mass, and the acidvalue of the resin in the resin varnish was 160.

Next. in a similar reaction vessel. a reaction was conducted in asimilar manner as in Production Example T3 except that 100 parts by massof the resin varnish, 29.6 parts by mass of copper acetate, and 14.5parts by mass of pivalic acid (acid value: 550 mgKOH/g) were used, toobtain a hydrolyzable resin composition T4 having a solid content of45.2% by mass.

The obtained hydrolyzable resin composition T4 was analyzed by GPC8220GPC″ available from TOSOH CORPORATION, eluent: dimethylformamide),and the weight average molecular weight of the hydrolyzable resincontained in the hydrolyzable resin composition T4 was 6500 in terms ofpolystyrene.

Table 1 and Table 2 show the charged amount (part by mass) of eachmaterial used for preparation of a hydrolyzable resin composition or aresin composition in Production Examples SI to S18 and T1 to T4, Gardnerviscosity (measured at 25° C. using a Gardner bubble viscometer) andsolid content (% by mass) of the obtained hydrolyzable resin compositionor resin composition, and the weight average molecular weight of thehydrolyzable resin or resin contained in the composition.

TABLE 1 Production example S1 S2 S3 S4 S5 S6 S7 S8 S9 T1 Charged (a)(a1) FM-0711 40 20 20 amount FM-0721 10 (part by X-24-8201 40 50 mass)Silicon-containing 30 monomer A Silicon-containing 30 monomer B (a2)TM-0701 20 Silicon-containing 30 monomer C Silicon-containing 20 monomerD (b)Metal-atom- M1 21.7 21.7 31.3 31.3 31.3 31.3 containing M2 28.428.4 monomer mixture M3 42.5 (c) MMA 32.3 32.3 18 18 26.4 21.4 26.4 1826.4 42.1 EA 43.9 17.9 25 15 29.5 29.5 18.5 35 39.5 37.9 2-MTA 5 ST 5Initiator AIBN 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 AMBN 3 0.8 1 1 42.5 2.5 2 5.5 2 Chain transfer α-methylstylene dimer 1.2 1.2 1.5 1.5 1.51.5 1.2 agent Gardner viscosity −U +U +U +R −W −T −V +T +W +E Solidcontent (% by mass) 45.7 45.1 45.2 45.0 45.8 45.3 45.6 45.3 45.6 44.8Weight average molecular weight 6800 8800 8200 7200 6400 6900 7000 77006000 6200

TABLE 2 Production example S10 S11 S12 S13 S14 S15 S16 Charged (a) (a1)FM-0711 35 30 amount X-24-8201 30 (part by (a2) TM-0701 mass)Silicon-containing monomer D (a3) FM-7711 10 5 10 FM-7721 20 10 10Silicon-containing 15 monomer E (a4) Silicon-containing 20 monomer FSilicon-containing monomer G (b)Metal-atom- M1 21.7 21.7 31.3 31.3 21.7containing monomer M2 28.4 mixture M3 42.5 (c) MMA 32.3 32.3 26.4 26.432.3 18 18 EA 47.9 37.9 44.5 39.5 17.9 25 15 2-MTA ST CHMA CHA M-90G AAMAA Initiator Kayaester O AIBN 2.5 2.5 2.5 2.5 2.5 2.5 2.5 AMBN 7.5 5 87.5 4 2.5 4.5 Chain transfer α-methylstylene dimer 2 1.5 2 1.5 1.2 agentGardner viscosity +W +U +R −W +V −V −T Solid content (% by mass) 46.246.1 46.4 45.8 45.6 45.4 45.6 Weight average molecular weight 5400 62005600 5500 9000 7200 6400 Production example S17 S18 T2 T3 T4 Charged (a)(a1) FM-0711 30 amount X-24-8201 (part by (a2) TM-0701 10 mass)Silicon-containing 38 monomer D (a3) FM-7711 10 FM-7721Silicon-containing monomer E (a4) Silicon-containing monomer FSilicon-containing 2 10 monomer G (b)Metal-atom- M1 31.3 containingmonomer M2 28.4 mixture M3 (c) MMA 26.4 18 42.1 11.17 EA 19.5 45 17.958.3 16.3 2-MTA ST CHMA 15 15 CHA 15 M-90G 10 30 AA 16.7 10.27 MAA 12.26Initiator Kayaester O 2.5 3.2 AIBN 2.5 2.5 2.5 AMBN 5.5 5 7 Chaintransfer α-methylstylene dimer 1.2 3 agent Gardner viscosity −T +W +EW-X Z2-Z3 Solid content (% by mass) 45.6 45.6 45.5 41.5 45.2 Weightaverage molecular weight 5600 6000 8600 8000 6500

Trade names and abbreviations shown in Table 1 and Table 2 are asfollows.

(1) FM-0711 (trade name, product of CHISSO CORPORATION):Silicon-containing polymerizable monomer wherein m=0, b=3, n=10, and R¹to R⁵ and R³¹ are methyl groups in the general formula (I′).

(2) FM-0721 (trade name, product of CHISSO CORPORATION):Silicon-containing polymerizable monomer wherein m=0, b=3, n=65, and R¹to R⁵ and R³¹ are methyl groups in the general formula (I′).

(3) X-24-8201 (trade name, product of Shin-Etsu Chemical Co., Ltd.):Silicon-containing polymerizable monomer wherein m=0, b=3, n=25, and R¹to R⁵ and R³¹ are methyl groups in the general formula (I′).

(4) Silicon-containing monomer A: Silicon-containing polymerizablemonomer wherein m=10, b=3, n=10, and R¹ to R⁵ and R³¹ are methyl groupsin the general formula (I′) which is a 1:1 (molar ratio) mixture ofthose wherein a is 2 and 3. (This monomer was sold by Nippon UnicarCompany Limited under the trade name “F2-254-04”.)

(5) Silicon-containing monomer B: Silicon-containing polymerizablemonomer wherein m=4, b=3, n=10, and R¹ to R⁵ and R³¹ are methyl groupsin the general formula (I′), which is a 1:1 (molar ratio) mixture ofthose wherein a is 2 and 3. (This monomer was sold by Nippon UnicarCompany Limited under the trade name “F2-254-14”.)

(6) TM-0701 (trade name, product of CHISSO CORPORATION):Silicon-containing polymerizable monomer wherein p=0, d=3. and R⁶ to R⁸and R³² are methyl groups in the general formula (II′).

(7) Silicon-containing monomer C: Silicon-containing polymerizablemonomer wherein p=0, d=3, R⁶ to R⁷ and R³² are methyl groups, and R⁸ isR^(a) (x=3, R²³ to R²⁷ are methyl groups) in the general formula (II′).(This monomer was sold by Nippon Unicar Company Limited under the tradename “F2-302-01”.)

(8) Silicon-containing monomer D: Silicon-containing polymerizablemonomer wherein p=10 d=3, R⁶ to R⁷ and R³² are methyl groups, and R⁸ isR^(a) (x=3, R²³ to R²⁷ are methyl groups) in the general formula (II′),which is a 1:1 (molar ratio) mixture of those wherein c is 2 and 3.(This monomer was sold by Nippon Unicar Company Limited under the tradename “F2-302-04”.)

(9) FM-7711 (trade name, product of CHISSO CORPORATION):Silicon-containing polymerizable monomer wherein q and s=0, f and g=3,r=10, and R⁹ to R¹², R³³ and R³⁴ are methyl groups in the generalformula (III′).

(10) FM-7721 (trade name, product of CHISSO CORPORATION):Silicon-containing polymerizable monomer wherein q and s=0, f and g=3,r=65, and R⁹ to R¹², R³³ and R³⁴ are methyl groups in the generalformula (III′).

(11) Silicon-containing monomer E: Silicon-containing polymerizablemonomer wherein q and s=10, f and g=3, r=10, and R⁹ to R¹², R³³ and R³⁴are methyl groups in the general formula (III′), which is a 1:1 (molarratio) mixture of those wherein e and h are 2 and 3. (This monomer wassold by Nippon Unicar Company Limited under the trade name “F2-354-04”.)

(12) Silicon-containing monomer F: Silicon-containing polymerizablemonomer wherein t and u=0, j and k=3, v and w=3, and R¹³ to R²², R³⁵ andR³⁶ are methyl groups in the general formula (IV′). (This monomer wassold by Nippon Unicar Company Limited under the trade name “F2-312-01”.)

(13) Silicon-containing monomer G: Silicon-containing polymerizablemonomer wherein t and u=10, j and k=3, v and w=3, and R¹³ to R²², R³⁵and R³⁶ are methyl groups in the general formula (IV′), which is a 1:1(molar ratio) mixture of those wherein i and 1 are 2 and 3. (Thismonomer was sold by Nippon Unicar Company Limited under the trade name“F2-312-04”.)

(14) MMA: methyl methacrylate

(15) EA: ethyl acrylate

(16) 2-MTA: 2-methoxyethyl acrylate

(17) ST: styrene

(18) CHMA: cyclohexyl methacrylate

(19) CHA: cyclohexyl acrylate

(20) M-900: methoxypolyethyleneglycol methacrylate (NK ester M-90G,product of Shin-Nakamura Chemical Co., Ltd.)

(21) AA: acrylic acid

(22) MAA: methacrylic acid

(23) Kayaester O: t-butylperoxy-2-ethylhexanoate (product of KavakuAkuzo Corporation)

(24) AIBN: azobisisobutyronitrile

(25) AMBN: azobismethylbutyronitrile

Examples 1 to 38, Comparative Examples 1 to 24

According to the formulation (part by mass) of Tables 3 to 6,antifouling coating compositions were prepared by mixing thehydrolyzable resin compositions or resin compositions S1 to S18 and T1to T4 obtained in Production Examples S1 to S18 and T1 to T4, and otheringredients shown in Tables 3 to 6 using a high-speed disperser.

TABLE 3 Example Unit: part by mass 1 2 3 4 5 6 7 8 9 10 Hydrolyzable S184.0 resin composition S2 80.0 or resin S3 88.5 composition S4 73.5 S570.0 S6 88.0 76.5 S7 70.0 S8 85.0 S9 82.3 Cuprous oxide Antifoulingagent 1 Antifouling agent 2 Antifouling agent 3 Antifouling agent 4Antifouling agent 5 Titanium oxide Yellow iron oxide Azoic red pigmentPhthalocyanine blue Thermoplastic resin 1 16.5 20.0 Thermoplastic resin2 10.0 20.0 Thermoplastic resin 3 6.0 Thermoplastic resin 4 2.0Plasticizer 1 5.0 Plasticizer 2 13.5 Plasticizer 3 7.7 Plasticizer 4 1.5Barium sulfate Antisettling agent Xylene 10.0 10.0 10.0 10.0 10.0 10.010.0 10.0 10.0 10.0 Total 100.0 100.0 100.0 100.0 100.0 100.0 100.0100.0 100.0 100.0 Total amount of thermoplastic resin 15.6 27.7 3.7 49.962.4 5.0 62.7 13.0 20.5 39.0 and plasticizer per 100 parts by mass ofresin (solid content) (part by mass) Specific gravity (g/ml) 1.01 1.001.00 1.00 1.04 1.00 1.00 1.01 1.02 1.03 Example Unit: part by mass 11 1213 14 15 16 17 18 19 Hydrolyzable S1 68.0 resin composition S2 63.0 orresin S3 55.0 composition S4 65.0 61.0 S5 76.5 S6 62.0 S7 78.1 68.0 S8S9 Cuprous oxide 3.0 Antifouling agent 1 2.0 3.0 Antifouling agent 2 2.0Antifouling agent 3 2.0 Antifouling agent 4 4.5 2.0 Antifouling agent 52.0 2.0 Titanium oxide 2.0 2.0 2.0 2.0 2.0 Yellow iron oxide 1.0 Azoicred pigment 14.0 3.0 4.0 Phthalocyanine blue 4.0 4.0 Thermoplastic resin1 5.3 10.0 4.0 Thermoplastic resin 2 15.0 10.0 Thermoplastic resin 312.0 14.0 8.0 Thermoplastic resin 4 5.0 11.0 Plasticizer 1 12.0Plasticizer 2 4.6 5.0 Plasticizer 3 4.0 8.0 Plasticizer 4 11.0 Bariumsulfate 3.0 Antisettling agent 2.0 2.0 2.0 2.0 2.0 Xylene 10.0 10.0 10.010.0 4.0 12.0 11.0 12.0 10.0 Total 100.0 100.0 100.0 100.0 100.0 100.0100.0 100.0 100.0 Total amount of thermoplastic resin 95.2 85.5 27.825.7 88.5 32.2 58.3 39.2 29.0 and plasticizer per 100 parts by mass ofresin (solid content) (part by mass) Specific gravity (g/ml) 1.02 1.051.03 1.05 1.10 1.04 1.07 1.09 1.07

TABLE 4 Example Unit: part by mass 20 21 22 23 24 25 26 27 28 29Hydrolyzable S10 85.0 84.0 resin composition S11 70.0 or resin S12 70.0composition S13 88.0 S14 80.0 S15 82.3 S16 73.5 S17 76.5 S18 88.5Cuprous oxide Antifouling agent 1 Antifouling agent 2 Antifouling agent3 Antifouling agent 4 Antifouling agent 5 Titanium oxide Yellow ironoxide Azoic red pigment Phthalocyanine blue Thermoplastic resin 1 20.016.5 Thermoplastic resin 2 20.0 10.0 Thermoplastic resin 3 6.0Thermoplastic resin 4 2.0 Plasticizer 1 5.0 Plasticizer 2 13.5Plasticizer 3 7.7 Plasticizer 4 1.5 Barium sulfate Antisettling agentXylene 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 Total 100.0100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 Total amount ofthermoplastic resin 12.7 62.0 61.6 5.0 27.4 20.6 49.2 38.7 3.7 15.5 andplasticizer per 100 parts by mass of resin (solid content) (part bymass) Specific gravity (g/ml) 1.01 1.00 1.04 1.00 1.00 1.02 1.00 1.031.00 1.01 Example Unit: part by mass 30 31 32 33 34 35 36 37 38Hydrolyzable S10 61.0 resin composition S11 63.0 68.0 or resin S12 62.0composition S13 55.0 S14 78.1 68.0 S15 65.0 S16 76.5 S17 S18 Cuprousoxide 3.0 Antifouling agent 1 2.0 3.0 Antifouling agent 2 2.0Antifouling agent 3 2.0 Antifouling agent 4 4.5 2.0 Antifouling agent 52.0 2.0 Titanium oxide 2.0 2.0 2.0 2.0 2.0 Yellow iron oxide 1.0 Azoicred pigment 14.0 3.0 4.0 Phthalocyanine blue 4.0 4.0 Thermoplastic resin1 5.3 10.0 4.0 Thermoplastic resin 2 15.0 10.0 Thermoplastic resin 312.0 14.0 8.0 Thermoplastic resin 4 5.0 Plasticizer 1 12.0 11.0Plasticizer 2 4.6 5.0 Plasticizer 3 4.0 8.0 Plasticizer 4 11.0 Bariumsulfate 3.0 Antisettling agent 2.0 2.0 2.0 2.0 2.0 Xylene 10.0 10.0 10.010.0 4.0 12.0 11.0 12.0 10.0 Total 100.0 100.0 100.0 100.0 100.0 100.0100.0 100.0 100.0 Total amount of thermoplastic resin 92.8 84.7 27.825.8 87.3 31.9 56.8 38.2 29.0 and plasticizer per 100 parts by mass ofresin (solid content) (part by mass) Specific gravity (g/ml) 1.02 1.051.03 1.05 1.10 1.04 1.08 1.09 1.07

TABLE 5 Comparative example Unit: part by mass 1 2 3 4 5 6 7 8 9 10 11Hydrolyzable S1 90.0 57.0 resin composition S2 90.0 or resin S3 90.0composition S4 90.0 S5 90.0 S6 90.0 S7 90.0 S8 90.0 S9 90.0 T1 90.0Cuprous oxide Antifouling agent 1 Antifouling agent 2 Antifouling agent3 Antifouling agent 4 Titanium oxide Yellow iron oxide Azoic red pigmentPhthalocyanine blue Thermoplastic resin 1 19.0 Thermoplastic resin 2Thermoplastic resin 3 Thermoplastic resin 4 Plasticizer 1 14.0Plasticizer 2 Plasticizer 3 Plasticizer 4 Barium sulfate Antisettlingagent Xylene 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0Total 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0Total amount of thermoplastic resin 0 126.7 0 0 0 0 0 0 0 0 0 andplasticizer per 100 parts by mass of resin (solid content) (part bymass)

TABLE 6 Comparative example Unit: part by mass 12 13 14 15 16 17 18 1920 21 22 23 24 Hydrolyzable S10 90.0 resin composition S11 90.0 55.0 orresin S12 90.0 composition S13 90.0 S14 90.0 S15 90.0 S16 90.0 S17 90.0S18 90.0 T2 90.0 T3 62.0 T4 57.0 Cuprous oxide 5.0 Zinc oxide 4.0Antifouling agent 1 2.0 Antifouling agent 2 2.0 Antifouling agent 3 2.0Antifouling agent 4 2.0 Titanium oxide 3.0 Phthalocyanine blue 2.0 Azoicred pigment 2.0 Red iron oxide 4.0 5.0 Thermoplastic resin 1 5.0 5.0Thermoplastic resin 2 15.0 Thermoplastic resin 3 3.0 3.0 Thermoplasticresin 4 Plasticizer 1 Plasticizer 2 Plasticizer 3 20.0 Plasticizer 4 3.03.0 Antisettling agent 2.0 2.0 Xylene 10.0 10.0 10.0 10.0 10.0 10.0 10.010.0 10.0 10.0 10.0 11.0 11.0 Total 100.0 100.0 100.0 100.0 100.0 100.0100.0 100.0 100.0 100.0 100.0 100.0 100.0 Total amount of thermoplasticresin 0 0 138.0 0 0 0 0 0 0 0 0 23 25 and plasticizer per 100 parts bymass of resin (solid content) (part by mass) Specific gravity (g/ml)1.19 1.23

The details of ingredients described in Tables 3 to 6 are as follows.

-   [1] cuprous oxide: product of NC Tech Co., Ltd. “NC-301”-   [2] zinc oxide: “zinc oxide Type 2” product of SAKAI CHEMICAL    INDUSTRY CO., LTD.-   [3] antifouling agent 1: ZPT (zinc pyrithione) (“Zinc Omadine”    product of Arch Chemicals)-   [4] antifouling agent 2: CuPT (copper pyrithione) (“Copper Omadine”    product of Arch Chemicals)-   [5] antifouling agent 3:    1,1-dichloro-N-[(dimethylamino)sulfonyl]-1-fluoro-N-(4-methylphenyl)methanesulfenamide    (“Preventol A5S” product of LANXESS)-   [6] antifouling agent 4:    4,5-dichloro-2-n-octyl-4-isothiazoline-3-one    (4,5-dichloro-2-n-octyl-3(2H)isothiazolone) (“Sea-Nine 211” product    of Rohm and Haas Company)-   [7] antifouling agent 5:    4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile    (“Econea” product of Janssen PMP)-   [8] titanium oxide: “TI-PURE R-900” product of Du Pont Kabushiki    Kaisha-   [9] yellow iron oxide: “TAROX synthetic iron oxide LL-XLO” product    of Titan Kogyo, Ltd.-   [10] azoic red pigment: “FUJI FAST RED 2305A” product of Fuji    Pigment CO., Ltd.-   [11] phthalocyanine blue: “CYANINE BLUE G-105” product of Sanyo    Color Works-   [12] red iron oxide: “Toda Color KN-R” product of Toda Kogyo Corp.

[13] thermoplastic resin 1: chlorinated paraffin (“TOYOPARAX A50”product of TOSOH CORPORATION)

-   [14] thermoplastic resin 2: polyvinyl ether (“Lutonal A25” product    of BASF Japan Ltd.)-   [15] thermoplastic resin 3: rosin (“WW rosin” product of ARAKAWA    CHEMICAL INDUSTRIES. LTD.)-   [16] thermoplastic resin 4: vinyl chloride-isobutylvinyl ether    copolymer (“Laroflex MP25” product of BASF Japan Ltd.)-   [17] plasticizer 1: DOP (dioctyl phthalate) (“DOP” product of    MITSUBISHI GAS CHEMICAL COMPANY INC)-   [18] plasticizer 2: DIDP (diisodecyl phthalate) (“DIDP” product of    CHISSO CORPORATION)-   [19] plasticizer 3: TCP (tricresyl phosphate) (“TCP” product of    DAIHACHI CHEMICAL INDUSTRY CO., LTD.)

[20] plasticizer 4: triaryl phosphate (“Reofos 65” product of AJINOMOTOCO INC,)

-   [21] barium sulfate: “Barite powder FBA” product of Naigai Talc Co.,    Ltd.-   [22] anti-settling agent: “DISPARLON A600-20X” product of KUSUMOTO    CHEMICALS, Ltd.

For antifouling films respectively formed from the antifouling coatingcompositions thus obtained, the long-term antifouling property,adherence with a base, crack resistance, polishing property andtransparency were evaluated according to the following evaluationmethods. The evaluation results are shown in Tables 7 to 10.

(1) Long-Term Antifouling Property

An obtained antifouling coating composition was applied on a blast platepreviously coated with an antirust paint so that the dry film thicknesswas 300 um, and dried by leaving it still in a room for two days andnights, to obtain a test plate having an antifouling film. The obtainedtest plate was subjected to an organism adhesion test using anexperimental raft installed at a marine laboratory of NIPPON PAINTMARINE COATINGS CO., Ltd. in Tamano, Okayama Prefecture, Japan, and theantifouling property was evaluated. In the tables, the number of monthsindicates the term in which the raft is dipped. The numerical values inthe tables represent the proportion (%) of organism adhesion area in thecoating film area (visually determined) and 15% or less was determinedas acceptable.

(2) Adherence with a Base (Grid Adhesion Test)

Using a test plate A that is obtained by applying an obtainedantifouling coating composition on a blast plate previously coated withan antirust paint so that the dry film thickness was 150 um, and dryingby leaving it still in a room for two days and nights; and a test plateB that is obtained by applying the same antifouling coating compositionas used in formation of the coating film on a surface of a coating filmof a substrate obtained by dipping the test plate A in sterilized andfiltered sea water for 3 months and leaving it still in a room for onenight and day so that the dry film thickness was 150 um, and drying byleaving it still in a room for two days and nights, a grid adhesion test(gap interval 2 mm. cell number 25) was conducted in conformance withJIS K 5600.5.6. The numerical values in the tables represent a score ofa test result evaluated in accordance with the following criteria.

-   Score 10: Each scratch is thin and smooth in both sides. and has no    peeling at an intersection of the scratch and in each square.-   Score 8: Slight peeling is observed at an intersection of scratch,    no peeling is observed in each square, and the area of a defected    part is within 5% of the entire square area.-   Score 6: Peeling is observed on both sides and at an intersection of    scratch, and the area of a defected part is 5 to 15% of the entire    square area.-   Score 4: The width of peeling due to scratch is large, and the area    of a defected part is 15 to 35% of the entire square area.-   Score 2: The width of peeling due to scratch is larger than that of    score 4, and the area of a defected part is 35 to 65% of the entire    square area.-   Score 0: The area of peeling is 65% or more of the entire square    area.

(3) Crack Resistance

-   -   (a) Crack resistance against dipping in sea water (Evaluation of        condition of coating film after dipping in sea water)

The state of a coating film of the test plate after dipping the raft for6 months in the long-term antifouling property test was observed byvisual check and rubbing, and evaluated. The state where no crack wasobserved was evaluated as A, and the state where a crack was observedwas evaluated as B.

-   -   (b) Crack resistance against repeated drying and wetting (drying        and wetting alternating test)

An obtained antifouling coating composition was applied on a blast platepreviously coated with an antirust paint so that the dry film thicknesswas 300 μm, and dried by leaving it still in a room for two days andnights, to obtain a test plate having an antifouling film. The obtainedtest plate was dipped in sea water of 40° C. for 1 week, and dried in aroom for 1 week, and a drying and wetting alternating test including theabove operations as one cycle was repeated up to the 20th cycle. When acrack occurred in the coating film during the test, the test ended atthe point of time when the crack occurred. and the cycle number at thatpoint was recorded in the table. The sample where no crack occurred evenafter 20 cycles was evaluated as A.

(4) Polishing Property (Coating Film Exhausted Amount (Polishing Speed)Test)

An obtained antifouling coating composition was applied on a blast platepreviously coated with an antirust paint so that the dry film thicknesswas 300 μm, and dried by leaving it still in a room for two days andnights, to obtain a test plate having an antifouling film. The testplate was pasted on a lateral face of a cylinder having a diameter of750 mm and a length of 1200 mm. and continuously rotated in sea water ata circumferential velocity of 15 knots for 24 months, and the coatingfilm exhausted amount of the test plate was measured every 3 months(accumulated reduction amount [μm] of coating film thickness).

(5) Transparency of Coating Film

An obtained antifouling coating composition was applied on a glass plateof 130 mm wide×100 mm long×2.0 mm thick so that the dry film thicknesswas 150 μm by using an applicator, and dried by leaving it still in aroom for one night and day, to obtain a test plate having an antifoulingfilm. The test plate was put on newspaper, and transparency of thecoating film was visually evaluated in accordance with the followingcriteria.

-   A: Completely transparent, and characters on the newspaper can be    easily recognized.-   B: Slightly transparent, and characters on the newspaper can be    slightly recognized.-   C: Completely masked, and characters on the newspaper cannot be    recognized.

TABLE 7 Example 1 2 3 4 5 6 7 8 9 10 Long-term  3 months 0 0 0 0 0 0 0 00 0 antifouling  6 months 0 0 0 0 0 0 0 0 0 0 property 12 months 5 0 0 00 0 0 0 0 0 [organism 18 months 10 0 5 5 0 0 0 5 0 0 adhesion area 24months 15 10 10 10 10 10 10 10 10 10 (%)] Adherence with Test plate A 1010 10 10 10 10 10 10 10 10 base (Grid Test plate B 10 10 10 10 10 10 1010 10 10 adhesion test) Crack resistance Dipping in A A A A A A A A A Asea water Repeated A A A A A A A A A A drying and wetting Polishing  3months 13 15 14 31 35 17 27 42 51 19 property  6 months 33 29 32 54 7040 55 77 99 36 [coating film  9 months 48 41 51 73 104 61 74 108 140 52exhausted 12 months 67 59 70 96 133 82 96 136 175 68 amount (μm)] 15months 85 72 89 121 161 103 121 161 216 83 18 months 104 89 105 144 192126 144 191 252 100 21 months 127 105 123 170 220 149 169 217 291 118 24months 145 121 142 193 249 172 192 250 — 135 Transparency of coatingfilm A — A A — A A A A — Example 11 12 13 14 15 16 17 18 19 Long-term  3months 0 0 0 0 0 0 0 0 0 antifouling  6 months 0 0 0 0 0 0 0 0 0property 12 months 0 0 0 0 0 0 0 0 0 [organism 18 months 0 5 0 0 5 0 0 00 adhesion area 24 months 10 10 0 0 10 0 0 0 0 (%)] Adherence with Testplate A 10 10 10 10 10 10 10 10 10 base (Grid Test plate B 10 10 10 1010 10 10 10 10 adhesion test) Crack resistance Dipping in A A A A A A AA A sea water Repeated A A A A A A A A A drying and wetting Polishing  3months 19 44 17 50 11 22 42 11 17 property  6 months 38 77 33 99 22 4673 26 34 [coating film  9 months 56 109 45 150 33 68 104 40 46 exhausted12 months 77 143 58 191 42 86 136 53 59 amount (μm)] 15 months 96 179 73242 54 110 170 67 74 18 months 116 211 87 293 67 134 200 82 88 21 months139 248 100 — 80 159 236 97 102 24 months 160 281 115 — 92 179 267 112117 Transparency of coating film A — A A — — — — —

TABLE 8 Example 20 21 22 23 24 25 26 27 28 29 Long-term  3 months 0 0 00 0 0 0 0 0 0 antifouling  6 months 0 0 0 0 0 0 0 0 0 0 property 12months 0 0 0 0 0 0 0 0 0 0 [organism 18 months 10 0 0 0 0 0 0 0 0 10adhesion area 24 months 15 5 0 0 0 0 0 0 0 15 (%)] Adherence with Testplate A 10 10 10 10 10 10 10 10 10 10 base (Grid Test plate B 10 10 1010 10 10 10 10 10 10 adhesion test) Crack resistance Dipping in A A A AA A A A A A sea water Repeated A A A A A A A A A A drying and wettingPolishing  3 months 12 13 43 23 18 21 30 29 30 19 property  6 months 2735 85 45 32 39 55 56 59 39 [coating film  9 months 43 54 127 67 45 57 7983 86 57 exhausted 12 months 58 71 171 90 61 80 106 112 114 75 amount(μm)] 15 months 71 89 212 114 79 98 132 139 142 94 18 months 85 108 251141 98 122 154 162 172 114 21 months 101 126 292 165 117 143 179 185 200136 24 months 116 145 — 188 133 164 204 213 228 153 Transparency ofcoating film A — — — A A A — A — Example 30 31 32 33 34 35 36 37 38Long-term  3 months 0 0 0 0 0 0 0 0 0 antifouling  6 months 0 0 0 0 0 00 0 0 property 12 months 0 0 0 0 0 0 0 0 0 [organism 18 months 0 0 0 0 00 0 0 0 adhesion area 24 months 5 0 0 0 0 0 0 0 0 (%)] Adherence withTest plate A 10 10 10 10 10 10 10 10 10 base (Grid Test plate B 10 10 1010 10 10 10 10 10 adhesion test) Crack resistance Dipping in A A A A A AA A A sea water Repeated A A A A A A A A A drying and wetting Polishing 3 months 18 21 14 37 16 16 15 40 14 property  6 months 42 38 24 69 3037 30 79 24 [coating film  9 months 61 57 34 102 43 53 46 118 34exhausted 12 months 79 78 46 137 58 69 61 158 47 amount (μm)] 15 months99 97 59 170 73 85 75 199 60 18 months 119 117 73 198 89 103 92 240 7421 months 138 139 86 230 103 121 107 281 88 24 months 158 158 100 262118 138 122 — 102 Transparency of coating film — — A A — — — — —

TABLE 9 Comparative example 1 2 3 4 5 6 7 8 9 10 11 Long-term  3 months0 0 0 0 0 0 0 0 0 0 100 antifouling  6 months 0 0 0 0 0 0 0 0 0 0 100property 12 months 5 10 0 0 0 0 0 0 0 0 100 [organism 18 months 10 30 55 5 0 0 0 5 0 100 adhesion area 24 months 15 40 10 10 10 5 10 10 10 10100 (%)] Adherence with Test plate A 10 6 10 10 10 10 10 10 10 10 0 base(Grid Test plate B 8 6 6 6 6 10 10 8 8 10 0 adhesion test) Crackresistance Dipping in B A B B B B B B B B B sea water Repeated 10 A 1110 14 12 10 11 10 12 8 drying and wetting Polishing  3 months 17 9 12 1945 55 25 21 47 60 0 property  6 months 35 18 24 37 82 110 48 41 92 117 0[coating film  9 months 51 26 35 56 110 167 69 55 122 166 0 exhausted 12months 66 34 48 75 145 213 90 71 150 209 0 amount (μm)] 15 months 84 4360 94 181 269 111 91 177 261 0 18 months 102 52 74 110 213 — 134 108 205— 0 21 months 121 61 88 128 250 — 157 121 240 — 0 24 months 137 70 101147 284 — 180 142 283 — 0 Transparency of coating film — — — — — — — — —— A

TABLE 10 Comparative example 12 13 14 15 16 17 18 19 20 21 22 23 24Long-term  3 months 0 0 0 0 0 0 0 0 0 0 60 10 0 antifouling  6 months 00 0 0 0 0 0 0 0 0 100 40 30 property 12 months 0 0 10 0 0 0 0 0 0 0 10080 70 [organism 18 months 10 0 20 0 0 0 0 0 0 0 100 100 100 adhesionarea 24 months 15 5 40 0 0 0 0 0 0 0 100 100 100 (%)] Adherence withTest plate A 10 10 6 10 10 10 10 10 10 10 0 10 10 base (Grid Test plateB 10 10 4 10 10 10 10 10 10 10 0 10 10 adhesion test) Crack resistanceDipping in B B A B B B B B B B B A A sea water Repeated 10 10 A 14 10 1110 10 12 12 10 A A drying and wetting Polishing  3 months 17 12 13 66 2715 25 41 39 31 0 19 82 property  6 months 33 28 31 131 49 27 47 77 75 600 35 99 [coating film  9 months 50 41 45 196 72 38 70 113 112 89 0 51111 exhausted 12 months 67 53 58 264 97 51 96 152 150 117 0 71 124amount (μm)] 15 months 83 66 73 — 121 65 118 189 187 145 0 89 127 18months 100 79 87 — 148 81 145 220 217 175 0 107 129 21 months 117 92 101— 172 96 170 256 251 207 0 127 134 24 months 134 105 116 — 197 110 195291 287 231 0 144 137 Transparency of coating film — — — — — — — — — — AC C

As shown in Tables 7 to 10. antifouling films obtained from theantifouling coating compositions of examples are excellent in long-termantifouling property, adherence with a base, and crack resistance. Onthe other hand, antifouling films obtained from the antifouling, coatingcompositions of comparative examples were insufficient in long-termantifouling property, or lacked crack resistance or adherence with abase even though an excellent long-term antifouling property wasexhibited. Also, exclusion of a thermoplastic resin or a plasticizer canlead to an excess coating film exhausted amount (Comparative Examples 6and 15).

1. An antifouling coating composition comprising: a hydrolyzable resinhaving at least one kind of silicon-containing group selected from thegroup consisting of the groups represented by the following generalformulas (I), (II), (III) and (IV) and a metal-atom-containing groupcontaining a divalent metal atom M; and a thermoplastic resin and/or aplasticizer, wherein the total content of said thermoplastic resinand/or plasticizer is 3 to 100 parts by mass per 100 parts by mass ofsaid hydrolyzable resin:

[wherein a and b each independently represent an integer of 2 to 5, mrepresents an integer of 0 to 50, and n represents an integer of 3 to80; and R¹ to R⁵ each independently represent an alkyl group, an alkoxygroup, a phenyl group, a substituted phenyl group, a phenoxy group or asubstituted phenoxy group];

[wherein c and d each independently represent an integer of 2 to 5, andp represents an integer of 0 to 50; R⁶, R⁷ and R⁸ each independentlyrepresent an alkyl group, R^(a) or R^(b); wherein R^(a) represents

(wherein x represents an integer of 0 to 20; and R²³ to R²⁷ are the sameor different and each represent an alkyl group), and R^(b) represents

[wherein y represents an integer of 1 to 20; and R²⁸ and R²⁹ are thesame or different and each represent an alkyl group)];

[wherein e, f, g and h each independently represent an integer of 2 to5, q and s each independently represent an integer of 0 to 50, and rrepresents an integer of 3 to 80; and R⁹ to R¹² each independentlyrepresent an alkyl group, an alkoxy group, a phenyl group, a substitutedphenyl group, a phenoxy group or a substituted phenoxy group]; and

[wherein i, j, k and l each independently represent an integer of 2 to5, t and u each independently represent an integer of 0 to 50, and v andw each independently represent an integer of 0 to 20; and R¹³ to R²² arethe same or different and each represent an alkyl group].
 2. Theantifouling coating composition according to claim 1, wherein saidmetal-atom-containing group is at least one kind of group selected fromthe group consisting of the groups represented by the following generalformulas (V) and (VI):

[wherein M represents a divalent metal atom, and R³⁰ represents anorganic acid residue or an alcohol residue]; and

[wherein M represents a divalent metal atom].
 3. The antifouling coatingcomposition according to claim 1, wherein said hydrolyzable resincomprises a constituent unit derived from at least one kind ofsilicon-containing polymerizable monomer (a) selected from the groupconsisting of a monomer (a1) represented by the following generalformula (I′), a monomer (a2) represented by the following generalformula (II′), a monomer (a3) represented by the following generalformula (III′) and a monomer (a4) represented by the following generalformula (IV′), and a constituent unit derived from ametal-atom-containing polymerizable monomer (b) containing a divalentmetal atom M:

[wherein R³¹ represents a hydrogen atom or a methyl group, and a, b, m,n and R¹ to R⁵ represent the same meaning as previously mentioned];

[wherein R³² represents a hydrogen atom or a methyl group, and c, d, pand R⁶ to R⁸ represent the same meaning as previously mentioned];

[wherein R³³ and R³⁴ represent a hydrogen atom or a methyl group, and e,f, g, h, q, r, s and R⁹ to R¹² represent the same meaning as previouslymentioned]; and

[wherein R³⁵ and R³⁶ represent a hydrogen atom or a methyl group, and i,j, k, l, t, u, v, w and R¹³ to R²² represent the same meaning aspreviously mentioned].
 4. The antifouling coating composition accordingto claim 3, wherein said metal-atom-containing polymerizable monomer (b)includes at least one kind selected from the group consisting of amonomer (b1) represented by the following general formula (V′) and amonomer (b2) represented by (VI′):

[wherein R³⁷ represents a hydrogen atom or a methyl group, and M and R³⁰represent the same meaning as previously mentioned]; and

[wherein R³⁸ and R³⁹ represent a hydrogen atom or a methyl group, and Mrepresents the same meaning as previously mentioned].
 5. The antifoulingcoating composition according to claim 3, wherein the ratio between thecontent of said constituent unit derived from the silicon-containingpolymerizable monomer (a) and the content of said constituent unitderived from the metal-atom-containing polymerizable monomer (b)containing a divalent metal atom M is in the range of 30/70 to 90/10 bymass ratio.
 6. The antifouling coating composition according to claim 1,wherein said thermoplastic resin is at least one kind selected from thegroup consisting of chlorinated paraffin, polyvinyl ether, rosin and avinyl chloride-isobutylvinyl ether copolymer.
 7. The antifouling coatingcomposition according to claim 1, wherein said plasticizer is at leastone kind selected from the group consisting of a phthalate esterplasticizer and a phosphate ester plasticizer.
 8. The antifoulingcoating composition according to claim 1, containing 0 to 20 parts bymass of an antifouling agent per 100 parts by mass of the total amountof said hydrolyzable resin, said thermoplastic resin and saidplasticizer.
 9. An antifouling film formed from the antifouling coatingcomposition according to claim
 1. 10. A composite film having a primerfilm formed from an antirust paint, and an antifouling film formed fromthe antifouling coating composition according to claim 1, overlaid onsaid primer film.
 11. The composite film according to claim 10, furtherhaving an intermediate film formed on the entire or part of a surface ofsaid primer film between said primer film and said antifouling film. 12.The composite film according to claim 11, wherein said intermediate filmis a coating film formed from an antifouling coating compositioncontaining an antifouling agent.
 13. An in-water structure having theantifouling film according to claim
 10. 14. A ship having theantifouling film according to claim 9.